U.S. patent application number 15/003481 was filed with the patent office on 2016-05-19 for cellulose acylate film, novel compound, polarizing plate, and liquid-crystal display device.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Nobutaka FUKAGAWA, Hiroshi INADA, Yasukazu KUWAYAMA, Masaki NORO, Naozumi SHIRAIWA, Yingjie XU, Aiko YOSHIDA.
Application Number | 20160139303 15/003481 |
Document ID | / |
Family ID | 52393438 |
Filed Date | 2016-05-19 |
United States Patent
Application |
20160139303 |
Kind Code |
A1 |
YOSHIDA; Aiko ; et
al. |
May 19, 2016 |
CELLULOSE ACYLATE FILM, NOVEL COMPOUND, POLARIZING PLATE, AND
LIQUID-CRYSTAL DISPLAY DEVICE
Abstract
Disclosed is a cellulose acylate film containing a compound
having at least one connecting group selected from a group
consisting of a bivalent connecting group denoted by
--NH--(C.dbd.O)--O-- and a bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- in which R represents a hydrogen atom or a
substituent group, and at least one polar group which is a residue
of a compound having a C log P value of less than or equal to 0.85
(however, an aromatic hetero ring-containing group which is a
residue of a compound having a C log P value of less than or equal
to 0.85 is excluded from the polar group), in which an equivalent
weight U obtained as a value which is obtained by dividing a
molecular weight by the number of connecting groups included in one
molecule is less than or equal to 515.
Inventors: |
YOSHIDA; Aiko; (Kanagawa,
JP) ; SHIRAIWA; Naozumi; (Kanagawa, JP) ;
INADA; Hiroshi; (Kanagawa, JP) ; KUWAYAMA;
Yasukazu; (Kanagawa, JP) ; FUKAGAWA; Nobutaka;
(Kanagawa, JP) ; XU; Yingjie; (Kanagawa, JP)
; NORO; Masaki; (Kanagawa, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
52393438 |
Appl. No.: |
15/003481 |
Filed: |
January 21, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2014/069823 |
Jul 28, 2014 |
|
|
|
15003481 |
|
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Current U.S.
Class: |
359/507 ;
106/170.1; 106/170.28; 106/170.44 |
Current CPC
Class: |
C08L 1/284 20130101;
C07D 209/48 20130101; C07C 271/20 20130101; C07C 2601/14 20170501;
C07C 275/24 20130101; C08L 1/32 20130101; C08K 5/205 20130101; C08L
1/10 20130101; G02B 5/3033 20130101; C08L 1/10 20130101; C08K 5/315
20130101; C08L 1/32 20130101; G02B 1/14 20150115; C08K 5/21
20130101; C07C 275/26 20130101; G02F 1/133528 20130101; C07D
295/215 20130101; C08L 1/284 20130101; C08L 1/28 20130101; C08K
5/20 20130101; G02B 1/04 20130101; C08J 5/18 20130101; C07D 207/404
20130101; C08J 2301/10 20130101; C07C 271/24 20130101; C08L 79/08
20130101; C08L 1/28 20130101; C08L 79/08 20130101; C08L 79/08
20130101; C08L 79/08 20130101 |
International
Class: |
G02B 1/14 20060101
G02B001/14; C08J 5/18 20060101 C08J005/18; G02B 5/30 20060101
G02B005/30; G02F 1/1335 20060101 G02F001/1335; G02B 1/04 20060101
G02B001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 26, 2013 |
JP |
2013-156150 |
Claims
1. A cellulose acylate film containing a compound having at least
one connecting group selected from a group consisting of a bivalent
connecting group denoted by --NH--(C.dbd.O)--O- and a bivalent
connecting group denoted by --NH--(C.dbd.O)--NR-- in which R
represents a hydrogen atom or a substituent group, and at least one
polar group which is a residue of a compound having a C log P value
of less than or equal to 0.85, wherein an aromatic hetero
ring-containing group which is a residue of a compound having a C
log P value of less than or equal to 0.85 is excluded from the
polar group, and an equivalent weight U obtained as a value which
is obtained by dividing a molecular weight by the number of
connecting groups included in one molecule is less than or equal to
515.
2. The cellulose acylate film according to claim 1, wherein the
compound has at least one of the polar groups as a terminal
substituent group.
3. The cellulose acylate film according to claim 2, wherein the
polar group is selected from a group consisting of a cyano group, a
cyclic imide group, an alkoxy carbonyl group, a hydroxyl group, an
alkyl aminocarbonyl oxy group, an alkoxy carbonyl amino group, and
an alkyl aminocarbonyl amino group.
4. The cellulose acylate film according to claim 1, wherein the
compound is a compound denoted by Formula A described below, and
Q.sup.A-L.sup.1-X--C(.dbd.O)--NH-L.sup.2-Q.sup.B Formula A in
Formula A, X represents --O-- or --NR--, and R represents a
hydrogen atom or a substituent group; L.sup.1 and L.sup.2 each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, --NR.sup.1--, --S--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
types thereof; R.sup.1 represents a hydrogen atom or a substituent
group; Q.sup.A and Q.sup.B each independently represent a
substituent group, and at least one of Q.sup.A and Q.sup.B
represents the polar group or the terminal group included in the
polar group; and X represents --NR--, L.sup.1 represents a single
bond, and when Q.sup.A has a ring structure, the ring structure
included in Q.sup.A may be a ring structure formed along with R of
--NR--.
5. The cellulose acylate film according to claim 4, wherein the
compound denoted by Formula A is a compound denoted by Formula A-1
described below, and (Q.sup.1-L.sup.11-A-L.sup.21).sub.m-Z.sup.1
Formula A-1 in Formula A-1, L.sup.11 and L.sup.21 each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, --NR.sup.1--, --S--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
types thereof; R.sup.1 represents a hydrogen atom or a substituent
group; Q.sup.1 represents a substituent group, Z.sup.1 represents a
m-valent connecting group, A represents a single bond,
*--X--C(.dbd.O)--NH--, or *--NH--C(.dbd.O)--X--, * represents a
bonding position with respect to L.sup.21, X represents --O-- or
--NR--, and R represents a hydrogen atom or a substituent group; m
represents an integer in a range of 2 to 6, and a plurality of
Q.sup.1s, As, L.sup.11s and L.sup.21s may be identical to each
other or different from each other, respectively; and at least one
A represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--, and at
least one Q.sup.1 represents the polar group or the terminal group
included in the polar group.
6. The cellulose acylate film according to claim 5, wherein in
Formula A-1, the connecting group represented by Z.sup.1 is a chain
aliphatic group or a cyclic aliphatic group, or an aromatic
group.
7. The cellulose acylate film according to claim 5, wherein in
Formula A-1, at least one of L.sup.11, L.sup.21, Q.sup.1, and
Z.sup.1 has a ring structure.
8. The cellulose acylate film according to claim 5, wherein in
Formula A-1, the polar group represented by at least one of the
plurality of Q.sup.1s has a ring structure.
9. The cellulose acylate film according to claim 5, wherein in
Formula A-1, at least one of the plurality of Q.sup.1s is the
terminal group included in the polar group, and the terminal group
is an alkyl group.
10. The cellulose acylate film according to claim 5, wherein in
Formula A-1, at least one of the plurality of Q.sup.1s is the
terminal group included in the polar group, L.sup.11 adjacent to
Q.sup.1 which is the terminal group is a single bond, and the polar
group is configured of Q.sup.1 and A represented by
*--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--.
11. The cellulose acylate film according to claim 5, wherein in
Formula A-1, m is 2 or 3.
12. The cellulose acylate film according to claim 5, wherein in
Formula A-1, L.sup.21 of at least one constituent unit of a
plurality of constituent units denoted
(Q.sup.1-L.sup.11-A-L.sup.21) is a single bond, and in the
constituent unit, A represents *--NH--C(.dbd.O)--X-- and is bonded
to Z.sup.1 in a bonding position *.
13. The cellulose acylate film according to claim 1, wherein the
compound is selected from a group consisting of a compound denoted
by Formula A-4 described below and a compound denoted by Formula
A-5 described below, and ##STR00035## in Formulas A-4 and A-5,
L.sup.1a and L.sup.1b each independently represent a single bond,
or any one of an alkylene group, an arylene group, --O--, and
--C(--O)-- or a group formed of a combination of two or more
thereof; X represents --O-- or --NR--, and R represents a hydrogen
atom or a substituent group; a plurality of Xs may be identical to
each other or different from each other; Q.sup.1a and Q.sup.1b each
independently represent a cyano group, a hydroxyl group, a
succinimide group, a hexahydrophthalimide group, a methoxy carbonyl
group, an alkoxy carbonyl amino group, an alkyl aminocarbonyl oxy
group, an alkyl aminocarbonyl amino group, an alkyl group, a phenyl
group, or a benzyl group, or when adjacent L.sup.1a or L.sup.1b
represents a single bond, and X represents --NR--, Q.sup.1a and
Q.sup.1b each independently represent a morpholino group formed
along with R of --NR--; and at least one of Q.sup.1a and Q.sup.1b
represents the polar group or the terminal group included in the
polar group.
14. The cellulose acylate film according to claim 13, wherein the
compound is a compound denoted by Formula A-4 above.
15. The cellulose acylate film according to claim 13, wherein the
compound is a compound denoted by Formula A-5 above.
16. The cellulose acylate film according to claim 1, wherein a
content of the compound is in a range of 1 part by mass to 50 parts
by mass with respect to 100 parts by mass of cellulose acylate.
17. A polarizing plate, comprising: the cellulose acylate film
according to claim 1; and a polarizer.
18. A liquid-crystal display device, comprising: the polarizing
plate according to claim 17.
19. The liquid-crystal display device according to claim 18,
wherein the liquid-crystal display device includes the polarizing
plate at least on a visible side.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of PCT International
Application No. PCT/JP2014/069823 filed on Jul. 28, 2014, which
claims priority under 35 U.S.C .sctn.119(a) to Japanese Patent
Application No. 2013-156150 filed on Jul. 26, 2013. Each of the
above applications is hereby expressly incorporated by reference,
in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a cellulose acylate film,
and a polarizing plate and a liquid-crystal display device. In
particular, the present invention relates to a cellulose acylate
film which is useful as a polarizing plate protective film, and a
polarizing plate including the cellulose acylate film and a
liquid-crystal display device including the polarizing plate.
[0004] Further, the present invention relates to a novel compound
which is useful as an additive for a cellulose acylate film.
[0005] 2. Description of the Related Art
[0006] A cellulose acylate film has been widely used as an optical
compensation film, a protective film, a substrate film, and the
like of a display device such as a liquid-crystal display device.
In order to improve performance of such a cellulose acylate film,
adding an additive, for example, is proposed in JP2004-175971A and
JP2005-272566A.
SUMMARY OF THE INVENTION
[0007] Recently, a display device has been enlarged and thinned,
focusing on the application to a television, and according to this,
a cellulose acylate film configuring the display device has been
increasingly required to be thinned. In this regard, according to
the studies of the present inventors, it has been found that, in a
thinned liquid-crystal display device, surface hardness of the film
particularly affects performance of the liquid-crystal display
device performance. In particular, it has been found that surface
hardness of a protective film used in a surface of a polarizing
plate on a viewer side greatly affects the performance of the
liquid-crystal display device.
[0008] However, in JP2004-175971A, it is disclosed that strength of
the entire cellulose acylate film is able to be improved by adding
additives disclosed in JP2004-175971A, but improvement in the
surface hardness is not disclosed. In addition, in JP2005-272566A,
dynamic properties of the film are not disclosed at all.
[0009] An object of the present invention is to solve such problems
of the related art and to provide a cellulose acylate film having
excellent surface hardness.
[0010] As a result of intensive studies of the present inventors on
the basis of the object described above, it has been newly found
that a compound having a specific structure is blended with a
cellulose acylate film, and thus it is possible to improve surface
hardness of the cellulose acylate film, and it is possible to
provide a thinned cellulose acylate film having high surface
hardness. The present inventors have assumed that this is because
the compound which contains a connecting group described below at a
predetermined ratio and has a polar group has a mutual interaction
with respect to a local portion such as an ester bond or a hydroxyl
group of cellulose acylate or a molecular chain, and decreases free
volume, and thus contributes to improvement in the surface hardness
of the cellulose acylate film.
[0011] The present invention has been accomplished on the basis of
the knowledge described above.
[0012] According to one aspect of the present invention, there is
provided a cellulose acylate film containing a compound having at
least one connecting group selected from a group consisting of a
bivalent connecting group denoted by --NH--(C.dbd.O)--O-- and a
bivalent connecting group denoted by --NH--(C.dbd.O)--NR-- in which
R represents a hydrogen atom or a substituent group, and at least
one polar group which is a residue of a compound having a C log P
value of less than or equal to 0.85, in which an aromatic hetero
ring-containing group which is a residue of a compound having a C
log P value of less than or equal to 0.85 is excluded from the
polar group, and an equivalent weight U obtained as a value which
is obtained by dividing a molecular weight by the number of
connecting groups included in one molecule, that is, U=[(Molecular
Weight)/(Number of Connecting Groups Included in One Molecule)] is
less than or equal to 515.
[0013] Furthermore, the aromatic hetero ring-containing group
excluded from the polar group is a group which is the residue of
the compound having a C log P value of less than or equal to 0.85
and has an aromatic hetero ring. The aromatic hetero ring indicates
a ring structure having a hetero atom in an aromatic ring. Examples
of the aromatic hetero ring include a triazine ring.
[0014] In addition, in one aspect, the bivalent connecting group
denoted by --NH--(C.dbd.O)--O-- or --NH--(C.dbd.O)--NR-- may be
included in the polar group.
[0015] In one aspect, the compound has at least one of the polar
groups as a terminal substituent group.
[0016] In one aspect, the polar group is selected from a group
consisting of a cyano group, a cyclic imide group, an alkoxy
carbonyl group, a hydroxyl group, an alkyl aminocarbonyl oxy group,
an alkoxy carbonyl amino group, and an alkyl aminocarbonyl amino
group.
[0017] In one aspect, the compound is a compound denoted by Formula
A described below.
Q.sup.A-L.sup.1-X--C(.dbd.O)--NH-L.sup.2-Q.sup.B Formula A
[0018] [In Formula A, X represents --O-- or --NR--, and R
represents a hydrogen atom or a substituent group; L.sup.1 and
L.sup.2 each independently represent a single bond, or any one of
an alkylene group, an arylene group, --O--, --NR.sup.1--, --S--,
and --C(.dbd.O)-- or a group formed of a combination of two or more
types thereof; R.sup.1 represents a hydrogen atom or a substituent
group; Q.sup.A and Q.sup.B each independently represent a
substituent group, and at least one of Q.sup.A and Q.sup.B
represents the polar group or the terminal group included in the
polar group; and X represents --NR--, L.sup.1 represents a single
bond, and when Q.sup.A has a ring structure, the ring structure
included in Q.sup.A may be a ring structure formed along with R of
--NR--.]
[0019] In one aspect, the compound denoted by Formula A is a
compound denoted by Formula A-1 described below.
(Q.sup.1-L.sup.11-A-L.sup.21).sub.m-Z.sup.1 Formula A-1
[0020] [In Formula A-1, L.sup.11 and L.sup.21 each independently
represent a single bond, or any one of an alkylene group, an
arylene group, --O--, --NR.sup.1--, --S--, and --C(.dbd.O)-- or a
group formed of a combination of two or more types thereof; R.sup.1
represents a hydrogen atom or a substituent group; Q.sup.1
represents a substituent group, Z.sup.1 represents a m-valent
connecting group, A represents a single bond,
*--X--C(.dbd.O)--NH--, or *--NH--C(.dbd.O)--X--, * represents a
bonding position with respect to L.sup.21, X represents --O-- or
--NR--, and R represents a hydrogen atom or a substituent group; m
represents an integer in a range of 2 to 6, and a plurality of
Q.sup.1s, As, L.sup.11 and L.sup.21s may be identical to each other
or different from each other, respectively; and at least one A
represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--, and at
least one Q.sup.1 represents the polar group or the terminal group
included in the polar group.]
[0021] In one aspect, in Formula A-1, the connecting group
represented by Z.sup.1 is a chain aliphatic group or a cyclic
aliphatic group, or an aromatic group.
[0022] In one aspect, in Formula A-1, at least one of L.sup.11,
L.sup.21, Q.sup.1, and Z.sup.1 has a ring structure.
[0023] In one aspect, in Formula A-1, the polar group represented
by at least one of the plurality of Q.sup.1s has a ring
structure.
[0024] In one aspect, in Formula A-1, at least one of the plurality
of Q's is the terminal group included in the polar group, and the
terminal group is an alkyl group.
[0025] In one aspect, in Formula A-1, at least one of the plurality
of Q's is the terminal group included in the polar group, L.sup.11
adjacent to Q.sup.1 which is the terminal group is a single bond,
and the polar group is configured of Q.sup.1 and A represented by
*--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--.
[0026] In one aspect, in Formula A-1, m is 2 or 3.
[0027] In one aspect, in Formula A-1, L.sup.21 of at least one
constituent unit of a plurality of constituent units denoted by
(Q.sup.1-L.sup.11-A-L.sup.21) is a single bond, and in the
constituent unit, A represents *--NH--C(.dbd.O)--X-- and is bonded
to Z.sup.1 in a bonding position *.
[0028] In one aspect, the compound is selected from a group
consisting of a compound denoted by Formula A-4 described below and
a compound denoted by Formula A-5 described below.
##STR00001##
[0029] [In Formulas A-4 and A-5, L.sup.1a and L.sup.1b each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, and --C(.dbd.O)-- or a group formed
of a combination of two or more thereof; X represents --O-- or
--NR--, and R represents a hydrogen atom or a substituent group. A
plurality of Xs may be identical to each other or different from
each other; Q.sup.1a and Q.sup.1b each independently represent a
cyano group, a hydroxyl group, a succinimide group, a
hexahydrophthalimide group, a methoxy carbonyl group, an alkoxy
carbonyl amino group, an alkyl aminocarbonyl oxy group, an alkyl
aminocarbonyl amino group, an alkyl group, a phenyl group, or a
benzyl group, or when adjacent L.sup.1a or L.sup.1b represents a
single bond, and X represents --NR--, Q.sup.1a and Q.sup.1b each
independently represent a morpholino group formed along with R of
--NR--; and at least one of Q.sup.1a and Q.sup.1b represents the
polar group or the terminal group included in the polar group.]
[0030] In one aspect, a content of the compound in the cellulose
acylate film is in a range of 1 part by mass to 50 parts by mass
with respect to 100 parts by mass of cellulose acylate.
[0031] According to another aspect of the present invention, there
is provided a polarizing plate including the cellulose acylate
film; and a polarizer.
[0032] According to still another aspect of the present invention,
there is provided a liquid-crystal display device including the
polarizing plate.
[0033] In one aspect, the liquid-crystal display device includes
the polarizing plate at least on a visible side.
[0034] According to still another aspect of the present invention,
there is provided a compound denoted by Formula A-6 described below
and having an equivalent weight U of less than or equal to 515
obtained as a value which is obtained by dividing a molecular
weight by the number of connecting groups included in one
molecule.
##STR00002##
[0035] [In Formula A-6, Q.sup.2a and Q.sup.2b each independently
represent a cyano group, a methoxy carbonyl amino group, an ethoxy
carbonyl amino group, a 1-propoxy carbonyl amino group, a 2-propoxy
carbonyl amino group, a methyl aminocarbonyl oxy group, an ethyl
aminocarbonyl oxy group, a 1-propyl aminocarbonyl oxy group, a
2-propyl aminocarbonyl oxy group, an alkyl group, a phenyl group,
or a benzyl group, and at least one of Q.sup.2a and Q.sup.2b
represents a cyano group, a methoxy carbonyl amino group, an ethoxy
carbonyl amino group, a 1-propoxy carbonyl amino group, a 2-propoxy
carbonyl amino group, a methyl aminocarbonyl oxy group, an ethyl
aminocarbonyl oxy group, a 1-propyl aminocarbonyl oxy group, or a
2-propyl aminocarbonyl oxy group; L.sup.2a and L.sup.2b each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, and --C(.dbd.O)-- or a group formed
of a combination of two or more thereof; X represents --O-- or
--NR.sup.1--, and R.sup.1 represents a hydrogen atom or a
substituent group; and a plurality of Xs may be identical to each
other or different from each other.]
[0036] According to still another aspect of the present invention,
there is provided a compound denoted by Formula A-7 described below
and having an equivalent weight U of less than or equal to 515
obtained as a value which is obtained by dividing a molecular
weight by the number of bivalent connecting groups denoted by
--X--(C.dbd.O)--NH-- and included in one molecule.
##STR00003##
[0037] [In Formula A-7, one of Q.sup.3a and Q.sup.3b represents a
cyano group, a succinimide group, or a hexahydrophthalimide group,
and the other of Q.sup.3a and Q.sup.3b represents an alkyl group, a
phenyl group, or a benzyl group; L.sup.3a and L.sup.3b each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, and --C(.dbd.O)-- or a group formed
of a combination of two or more thereof; X represents --O-- or
--NR--, and R represents a hydrogen atom or a substituent group;
and a plurality of Xs may be identical to each other or different
from each other.]
[0038] According to still another aspect of the present invention,
there is provided a compound denoted by Formula A-8 described below
and having an equivalent weight U of less than or equal to 515
obtained as a value which is obtained by dividing a molecular
weight by the number of bivalent connecting groups denoted by
--X--(C.dbd.O)--NH-- and included in one molecule.
##STR00004##
[0039] [In Formula A-8, Q.sup.4a and Q.sup.4b each independently
represent a methoxy carbonyl amino group, an ethoxy carbonyl amino
group, a 1-propoxy carbonyl amino group, a 2-propoxy carbonyl amino
group, a methyl aminocarbonyl oxy group, an ethyl aminocarbonyl oxy
group, a 1-propyl aminocarbonyl oxy group, a 2-propyl aminocarbonyl
oxy group, an alkyl group, a phenyl group, or a benzyl group, and
at least one of Q.sup.4a and Q.sup.4b represents a methoxy carbonyl
amino group, an ethoxy carbonyl amino group, a 1-propoxy carbonyl
amino group, a 2-propoxy carbonyl amino group, a methyl
aminocarbonyl oxy group, an ethyl aminocarbonyl oxy group, a
1-propyl aminocarbonyl oxy group, or a 2-propyl aminocarbonyl oxy
group; L.sup.4a and L.sup.4b each independently represent a single
bond, or any one of an alkylene group, an arylene group, --O--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
thereof; X represents --O-- or --NR--, and R represents a hydrogen
atom or a substituent group; and a plurality of Xs may be identical
to each other or different from each other.]
[0040] According to still another aspect of the present invention,
there is provided a compound denoted by Formula A-9 described below
and having an equivalent weight U of less than or equal to 515
obtained as a value which is obtained by dividing a molecular
weight by the number of bivalent connecting groups denoted by
--X--(C.dbd.O)--NH-- and included in one molecule.
Q.sup.100-(L.sup.100-A.sup.100)m1-Q.sup.101 Formula A-9:
[0041] [In Formula A-9, L.sup.100 represents any one of a single
bond, an alkylene group, and
##STR00005##
represents a bonding position with respect to the other structure
configuring the compound denoted by Formula A-9, and one or more of
a plurality of L.sup.100s represent a group other than the single
bond; Q.sup.100 and Q.sup.101 each independently represent an alkyl
group, a hydroxyl group, or a cyano group; A.sup.100 represents
*--X--C(.dbd.O)--NH-- or *--NH--C(--O)--X--, * represents a bonding
position with respect to L.sup.100, X represents --O-- or --NR--,
and R represents a hydrogen atom or a substituent group; and m1
represents an integer in a range of 2 to 6.]
[0042] According to the present invention, it is possible to
provide a cellulose acylate film having high surface hardness.
Further, according to the present invention, it is possible to
provide a cellulose acylate film in which the yellowish film due to
light irradiation (photo-coloration properties) is suppressed, and
volatilization of the added compound decreases. By using such a
cellulose acylate film, it is possible to provide a high-quality
polarizing plate having high durability and a liquid-crystal
display device including the polarizing plate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 illustrates an example of a positional relationship
between a polarizing plate and a liquid-crystal display device
according to one aspect of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0044] Hereinafter, the present invention will be described in more
detail. Furthermore, in the present invention and in the present
specification, "to" is used as the meaning which includes the
numerical values before and after "to" as the lower limit value and
the upper limit value. In the present invention and in the present
specification, a "group" such as an alkyl group, unless otherwise
particularly stated, may have a substituent group, or may not have
a substituent group. Further, when the number of carbon atoms is
limited in a group, the number of carbon atoms indicates the number
of carbon atoms included in a substituent group.
[0045] In the present invention, a cellulose acylate film is a film
in which a content ratio of cellulose acylate is greater than or
equal to 50 mass % with respect to 100 mass % of the total amount
of film solid contents. The content ratio of the cellulose acylate
is preferably greater than or equal to 60 mass %, is more
preferably greater than or equal to 70 mass %, is even more
preferably greater than or equal to 80 mass %, and is still more
preferably greater than or equal to 85 mass %. The upper limit
value of the content ratio of the cellulose acylate, for example,
is less than or equal to 99 mass %, but is not particularly
limited. The cellulose acylate film of the present invention may be
in the shape of a laminated film of two or more cellulose acylate
films having different compounds, or may be in the shape of a
laminated film of the cellulose acylate film and a film or a layer
other than the cellulose acylate film. Examples of the film or the
layer other than the cellulose acylate film, which configures the
laminated film, are able to include various functional layers
specialized for a specific function. Examples of such a functional
layer include a hard coat layer described below, but are not
limited thereto.
[0046] The cellulose acylate film of the present invention contains
a compound having at least one connecting group selected from a
group consisting of a bivalent connecting group denoted by
--NH--(C.dbd.O)--O-- and a bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- in which R represents a hydrogen atom or a
substituent group, and at least one polar group which is a residue
of a compound having a C log P value of less than or equal to 0.85,
and in the compound, an equivalent weight U obtained as
U=[(Molecular Weight)/(Number of Connecting Groups Included in One
Molecule)] is less than or equal to 515.
[0047] The present inventors have considered that a decrease in the
free volume of the compound by a mutual interaction between the
connecting group included in the compound in a predetermined amount
and a local portion such as an ester bond or a hydroxyl group of
cellulose acylate or a molecular chain contributes to improvement
in the surface hardness of the cellulose acylate film. Further, the
present inventors have assumed that improvement in compatibility
between the cellulose acylate and the compound by the polar group
included in the compound along with the connecting group
contributes to strengthening a mutual interaction. By adding such a
compound, as described in the following examples, it is possible to
provide a cellulose acylate film having high surface hardness.
Therefore, the compound is useful as an additive for a cellulose
acylate film. Furthermore, as described above, an aromatic hetero
ring-containing group which is the residue of the compound having a
C log P value of less than or equal to 0.85 is excluded from the
polar group.
[0048] Hereinafter, the compound will be described in more
detail.
[0049] The compound includes at least one connecting group selected
from a group consisting of a bivalent connecting group denoted by
--NH--(C.dbd.O)--O-- and a bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- in which R represents a hydrogen atom or a
substituent group in one molecule. Examples of the substituent
group represented by R are able to include substituent groups
described below as a group of substituent groups T. The connecting
group is a group which is able to be obtained by the mutual
interaction with respect to the cellulose acylate. Then, the
compound includes the connecting group at a ratio where the
equivalent weight U obtained as U=[(Molecular Weight)/(Number of
Connecting Groups Included in One Molecule)] is less than or equal
to 515. A content ratio of the connecting group per one molecule
increases as the value of the equivalent weight U decreases.
According to the compound having the value of the equivalent weight
U of less than or equal to 515 and the polar group, it is possible
to obtain a cellulose acylate film having high surface hardness.
The value of the equivalent weight U is preferably less than or
equal to 450, is more preferably less than or equal to 420, and is
even more preferably less than or equal to 300. The lower limit
value is not particularly limited, but for example, is greater than
or equal to 100.
[0050] The compound includes at least one connecting group selected
from the group described above, preferably includes one or more
connecting groups, more preferably includes 1 to 15 connecting
groups, even more preferably includes 1 to 10 connecting groups,
and still more preferably includes 2 to 8 connecting groups, in one
molecule. When a plurality of connecting groups selected from the
group described above are included in one molecule of the compound,
all of the plurality of connecting groups may be identical to each
other or different from each other. It is more preferable that 2 to
6 connecting groups selected from the group described above are
included in one molecule. In this case, in one preferred aspect,
the compound includes two bivalent connecting group denoted by
--NH--(C.dbd.O)--O-- in one molecule. In another preferred aspect,
the compound includes one bivalent connecting group denoted by
--NH--(C.dbd.O)--O-- and one bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- in one molecule.
[0051] When a plurality of connecting groups selected from the
group described above are included in the compound, the connecting
groups may be connected through the other connecting group.
Preferably, the other connecting group exists between the
connecting groups selected from the group described above. Examples
of such a connecting group include the connecting group represented
by Z.sup.1 of Formula A-1 described below or the connecting group
represented by Z.sup.1. It is preferable that the connecting group
existing between the connecting groups selected from the group
described above has a chain structure, a branch structure, or a
ring structure from a viewpoint of improving the surface hardness
of the cellulose acylate film. It is more preferable that the
connecting group existing between the connecting groups selected
from the group described above is a connecting group having a chain
aliphatic group or a cyclic aliphatic group, or an aromatic group.
The ring structure may be a carbon ring or a hetero ring, and it is
preferable that the ring structure is a carbon ring. It is more
preferable that the ring structure is a cyclohexane ring which may
have a substituent group or a benzene ring which may have a
substituent group, and it is even more preferable that the ring
structure is a cyclohexane ring which may have a substituent group
or a non-substitutional benzene ring.
[0052] Examples of the substituent group include the group of
substituent groups T described below. In addition, unless otherwise
particularly stated, the substituent group in the present invention
is a substituent group selected from the group of substituent
groups T described below. Examples of the substituent group which
is substituted for the ring structure include an alkyl group having
1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a
1-propyl group, a 2-propyl group (an isopropyl group), and the
like, and preferably a methyl group), and an alkoxy group having 1
to 3 carbon atoms (for example, a methoxy group, an ethoxy group,
and the like).
[0053] Group of Substituent Groups T:
[0054] An alkyl group (preferably an alkyl group having 1 to 20
carbon atoms, more preferably an alkyl group having 1 to 12 carbon
atoms, particularly preferably an alkyl group having 1 to 8 carbon
atoms, and for example, a methyl group, an ethyl group, a 1-propyl
group, a 2-propyl group, a tert-butyl group, an n-octyl group, an
n-decyl group, an n-hexadecyl group, a cyclopropyl group, a
cyclopentyl group, a cyclohexyl group, and the like), an alkenyl
group (preferably an alkenyl group having 2 to 20 carbon atoms,
more preferably an alkenyl group having 2 to 12 carbon atoms,
particularly preferably an alkenyl group having 2 to 8 carbon
atoms, and for example, a vinyl group, an allyl group, a 2-butenyl
group, a 3-pentenyl group, and the like), an alkynyl group
(preferably an alkynyl group having 2 to 20 carbon atoms, more
preferably an alkynyl group having 2 to 12 carbon atoms,
particularly preferably an alkynyl group having 2 to 8 carbon
atoms, and for example, a propargyl group, a 3-pentynyl group, and
the like), an aryl group (preferably an aryl group having 6 to 30
carbon atoms, more preferably an aryl group having 6 to 20 carbon
atoms, particularly preferably an aryl group having 6 to 12 carbon
atoms, and for example, a phenyl group, a biphenyl group, a
naphthyl group, and the like), an amino group (preferably an amino
group having 0 to 20 carbon atoms, more preferably an amino group
having 0 to 10 carbon atoms, particularly preferably an amino group
having 0 to 6 carbon atoms, and for example, an amino group, a
methyl amino group, a dimethyl amino group, a diethyl amino group,
a dibenzyl amino group, and the like), an alkoxy group (preferably
an alkoxy group having 1 to 20 carbon atoms, more preferably an
alkoxy group having 1 to 12 carbon atoms, particularly preferably
an alkoxy group having 1 to 8 carbon atoms, and for example, a
methoxy group, an ethoxy group, a butoxy group, and the like), an
aryl oxy group (preferably an aryl oxy group having 6 to 20 carbon
atoms, more preferably an aryl oxy group having 6 to 16 carbon
atoms, particularly preferably an aryl oxy group having 6 to 12
carbon atoms, and for example, a phenyl oxy group, a 2-naphthyl oxy
group, and the like), an acyl group (preferably an acyl group
having 1 to 20 carbon atoms, more preferably an acyl group having 1
to 16 carbon atoms, particularly preferably an acyl group having 1
to 12 carbon atoms, and for example, an acetyl group, a benzoyl
group, a formyl group, a pivaloyl group, and the like), an alkoxy
carbonyl group (preferably an alkoxy carbonyl group having 2 to 20
carbon atoms, more preferably an alkoxy carbonyl group having 2 to
16 carbon atoms, particularly preferably an alkoxy carbonyl group
having 2 to 12 carbon atoms, and for example, a methoxy carbonyl
group, an ethoxy carbonyl group, and the like), an aryl oxy
carbonyl group (preferably an aryl oxy carbonyl group having 7 to
20 carbon atoms, more preferably an aryl oxy carbonyl group having
7 to 16 carbon atoms, particularly preferably an aryl oxy carbonyl
group having 7 to 10 carbon atoms, and for example, a phenyl oxy
carbonyl group, and the like), an acyl oxy group (preferably an
acyl oxy group having 2 to 20 carbon atoms, more preferably an acyl
oxy group having 2 to 16 carbon atoms, particularly preferably an
acyl oxy group having 2 to 10 carbon atoms, and for example, an
acetoxy group, a benzoyl oxy group, and the like), an acyl amino
group (preferably an acyl amino group having 2 to 20 carbon atoms,
more preferably an acyl amino group having 2 to 16 carbon atoms,
particularly preferably an acyl amino group having 2 to 10 carbon
atoms, and for example, an acetyl amino group, a benzoyl amino
group, and the like), an alkoxy carbonyl amino group (preferably an
alkoxy carbonyl amino group having 2 to 20 carbon atoms, more
preferably an alkoxy carbonyl amino group having 2 to 16 carbon
atoms, particularly preferably an alkoxy carbonyl amino group
having 2 to 12 carbon atoms, and for example, a methoxy carbonyl
amino group, and the like), an aryl oxy carbonyl amino group
(preferably an aryl oxy carbonyl amino group having 7 to 20 carbon
atoms, more preferably an aryl oxy carbonyl amino group having 7 to
16 carbon atoms, particularly preferably an aryl oxy carbonyl amino
group having 7 to 12 carbon atoms, and for example, a phenyl oxy
carbonyl amino group, and the like), a sulfonyl amino group
(preferably a sulfonyl amino group having 1 to 20 carbon atoms,
more preferably a sulfonyl amino group having 1 to 16 carbon atoms,
particularly preferably a sulfonyl amino group having 1 to 12
carbon atoms, and for example, a methane sulfonyl amino group, a
benzene sulfonyl amino group, and the like), a sulfamoyl group
(preferably a sulfamoyl group having 0 to 20 carbon atoms, more
preferably a sulfamoyl group having 0 to 16 carbon atoms,
particularly preferably a sulfamoyl group having 0 to 12 carbon
atoms, and for example, a sulfamoyl group, a methyl sulfamoyl
group, a dimethyl sulfamoyl group, a phenyl sulfamoyl group, and
the like), a carbamoyl group (preferably a carbamoyl group having 1
to 20 carbon atoms, more preferably a carbamoyl group having 1 to
16 carbon atoms, particularly preferably a carbamoyl group having 1
to 12 carbon atoms, and for example, a carbamoyl group, a methyl
carbamoyl group, a diethyl carbamoyl group, a phenyl carbamoyl
group, and the like), an alkyl thio group (preferably an alkyl thio
group having 1 to 20 carbon atoms, more preferably an alkyl thio
group having 1 to 16 carbon atoms, particularly preferably an alkyl
thio group having 1 to 12 carbon atoms, and for example, a methyl
thio group, an ethyl thio group, and the like), an aryl thio group
(preferably an aryl thio group having 6 to 20 carbon atoms, more
preferably an aryl thio group having 6 to 16 carbon atoms,
particularly preferably an aryl thio group having 6 to 12 carbon
atoms, an for example, a phenyl thio group, and the like), a
sulfonyl group (preferably a sulfonyl group having 1 to 20 carbon
atoms, more preferably a sulfonyl group having 1 to 16 carbon
atoms, particularly preferably a sulfonyl group having 1 to 12
carbon atoms, and for example, a mesyl group, a tosyl group, and
the like), a sulfinyl group (preferably a sulfinyl group having 1
to 20 carbon atoms, more preferably a sulfinyl group having 1 to 16
carbon atoms, particularly preferably a sulfinyl group having 1 to
12 carbon atoms, and for example, a methane sulfinyl group, a
benzene sulfinyl group, and the like), a urethane group, a ureido
group (preferably a ureido group having 1 to 20 carbon atoms, more
preferably a ureido group having 1 to 16 carbon atoms, particularly
preferably a ureido group having 1 to 12 carbon atoms, and for
example, a ureido group, a methyl ureido group, a phenyl ureido
group, and the like), a phosphoric amide group (preferably a
phosphoric amide group having 1 to 20 carbon atoms, more preferably
a phosphoric amide group having 1 to 16 carbon atoms, particularly
preferably a phosphoric amide group having 1 to 12 carbon atoms,
and for example, diethyl phosphoric amide, phenyl phosphoric amide,
and the like), a hydroxyl group, a mercapto group, a halogen atom
(for example, a fluorine atom, a chlorine atom, a bromine atom, and
an iodine atom), a cyano group, a sulfo group, a carboxyl group, a
nitro group, a hydroxamic acid group, a sulfino group, a hydrazino
group, an imino group, a heterocyclic group (preferably a
heterocyclic group having 1 to 30 carbon atoms, more preferably a
heterocyclic group having 1 to 12 carbon atoms in which examples of
a hetero atom includes a nitrogen atom, an oxygen atom, and a
sulfur atom, and specifically, for example, an imidazolyl group, a
pyridyl group, a quinolyl group, a furyl group, a piperidyl group,
a morpholino group, a benzooxazolyl group, a benzimidazolyl group,
a benzthiazolyl group, and the like), and a silyl group (preferably
a silyl group having 3 to 40 carbon atoms, more preferably a silyl
group having 3 to 30 carbon atoms, particularly preferably a silyl
group having 3 to 24 carbon atoms, and for example, a trimethyl
silyl group, a triphenyl silyl group, and the like).
[0055] The substituent groups may be further substituted. In
addition, when two or more substituent groups are used, the
substituent groups may be identical to each other or different from
each other. In addition, when it is possible, the substituent
groups may be connected to each other and may form a ring.
[0056] In JP2004-175971A described above, an additive for improving
toughness of the film is disclosed, but the present inventors have
examined the additive disclosed in JP2004-175971A, and have found
that the yellowish film occurs according to continuous light
irradiation (hereinafter, referred to as photo-coloration
properties) due to absorption at 275 nm or higher. In consideration
of this point, it is preferable that a compound used as an additive
for a cellulose acylate film does not cause the photo-coloration
properties of the film. From this viewpoint, in one aspect, it is
preferable that the compound is a compound allowing the cellulose
acylate film to which the compound is added to have low
photo-coloration properties. The present inventors have considered
that the structure of the connecting group, with which the
connecting group selected from the group described above is
connected to the other structure included in the compound, affects
the photo-coloration properties. The connecting group selected from
the group described above is connected to the other structure
configuring the compound by a nitrogen atom or an oxygen atom. It
is preferable that the connecting group is an alkylene group from a
viewpoint of suppressing the photo-coloration properties. The
details of the alkylene group are identical to those of the
alkylene group represented by L.sup.1 and L.sup.2 of Formula A
described below. In addition, it is preferable that in the
connecting group selected from the group described above, a
nitrogen atom or an oxygen atom is not directly bonded to an
aromatic ring from a viewpoint of suppressing the photo-coloration
properties. In addition, it is more preferable that two or more
connecting groups selected from the group described above are not
directly bonded to the same aromatic ring. According to such a
structure, it is possible to suppress expansion of a conjugate
structure in the molecules, and thus it is possible to obtain a
more excellent photo-coloration property suppression effect.
[0057] The compound includes a polar group along with the
connecting group selected from the group described above. Here, the
polar group is a residue of a compound having a C log P value of
less than or equal to 0.85. Here, P of C log P represents a
distribution coefficient in an n-octanol-water system, and is able
to be measured by using n-octanol and water, and an estimated value
is able to be obtained from the distribution coefficient by using a
C log P value estimation program (a C LOG P program incorporated in
PC Models manufactured by Daylight Chemical Information Systems
Inc.). The C log P value is calculated as the compound. In order to
calculate the C log P value, a target residue from which C log P is
obtained is input as complete molecules not as radicals or ions.
For example, residues B.sup.1 and B.sup.2 are determined as a
B.sup.1--H portion and a B.sup.2--H portion along with a hydrogen
atom. Practically, even when the compound has a structure which
does not exist, the C log P value is able to be obtained as a value
estimated by a calculating chemical method or an empirical
method.
[0058] The compound includes at least one polar group which is the
residue of the compound having a C log P value of less than or
equal to 0.85 in one molecule. It is considered that strengthening
a mutual interaction between the compound and the cellulose acetate
by including such a polar group contributes to improvement in the
surface hardness of the cellulose acylate film to be obtained. In
consideration of compatibility with respect to the cellulose
acylate, the number of polar groups included in one molecule is
preferably 1 to 3, and is more preferably 2 or 3. When a plurality
of polar groups are included in the compound, it is preferable that
at least one polar group exists as a terminal substituent group.
Alternatively, the polar group may be included in a substituent
group of the group represented by R of --NR--C(.dbd.O)--NH--. When
a cyano group is included in R, it is preferable that the cyano
group is bonded to a nitrogen atom configuring --NR-- through an
alkylene group (for example, an alkylene group having 1 to 3 carbon
atoms).
[0059] The C log P value described above is preferably less than or
equal to 0.50, is more preferably less than or equal to 0.30, and
is even more preferably less than or equal to 0. In addition, it is
more preferable that the C log P value of the polar group is
greater than or equal to -5.0 from a viewpoint of compatibility
with respect to the cellulose acylate. Specifically, examples of
the polar group include a cyano group, a cyclic imide group or a
chain imide group (for example, a phthalimide group, a succinimide
group, a hexahydrophthalimide group, and the like), a nitro group,
a hydroxyl group, a sulfone amide group, a carbon amide group, a
carboxyl group, an amino group, a monovalent substituent group
denoted by --(NR)n1-(C.dbd.O)--OR (here, R represents a hydrogen
atom or a substituent group, two Rs may be identical to each other
or different from each other, respectively, and n1 represents 0 or
1), an aminocarbonyl oxy group (--O--(C--O)--NRR, here, R
represents a hydrogen atom or a substituent group, and two Rs may
be identical to each other or different from each other,
respectively), and an aminocarbonyl amino group
(--NR--(C.dbd.O)--NRR, here, R represents a hydrogen atom or a
substituent group, and a plurality of Rs may be identical to each
other or different from each other, respectively). Preferably,
examples of the polar group include a cyano group, an imide group,
an alkoxy carbonyl group (--(C.dbd.O)--OR.sup.100, here, R.sup.100
represents an alkyl group), a hydroxyl group, an alkyl
aminocarbonyl oxy group (--O--(C.dbd.O)--NR--R.sup.100, here, R
represents a hydrogen atom or a substituent group, and R.sup.100
represents an alkyl group), an alkoxy carbonyl amino group
(--NR--(C.dbd.O)--OR.sup.100 (here, R represents a hydrogen atom or
a substituent group, and R.sup.100 represents an alkyl group), and
an alkyl aminocarbonyl amino group (--NR--(C--O)--NR--R.sup.100,
here, R represents a hydrogen atom or a substituent group, two Rs
may be identical to each other or different from each other,
respectively, and R.sup.100 represents an alkyl group).
[0060] A cyclic imide group is preferable as the imide group
described above. A succinimide group, a phthalimide group, and a
hexahydrophthalimide group are preferable as the cyclic imide
group.
[0061] In addition, it is preferable that the alkyl group
represented by R.sup.100 is an alkyl group having 1 to 3 carbon
atoms. It is more preferable that the alkyl aminocarbonyl oxy group
is a methyl aminocarbonyl oxy group in which R.sup.100 is a methyl
group, and R is a hydrogen atom. It is preferable that the alkoxy
carbonyl group is an alkoxy carbonyl group in which R.sup.100 is an
alkyl group having 1 to 3 carbon atoms, and it is more preferable
that the alkoxy carbonyl group is a methoxy carbonyl group in which
R.sup.100 is a methyl group. It is preferable that the alkoxy
carbonyl amino group is an alkoxy carbonyl amino group in which
R.sup.100 is an alkyl group having 1 to 3 carbon atoms, and it is
more preferable that the alkoxy carbonyl amino group is a methoxy
carbonyl amino group in which R.sup.100 is a methyl group. It is
preferable that the alkyl aminocarbonyl amino group is an alkyl
aminocarbonyl amino group in which R.sup.100 is an alkyl group
having 1 to 3 carbon atoms, and it is more preferable that the
alkyl aminocarbonyl amino group is a methyl aminocarbonyl amino
group in which R.sup.100 is a methyl group.
[0062] In one aspect, when the compound includes a polar group
selected from a group consisting of an alkyl aminocarbonyl oxy
group and an alkyl aminocarbonyl amino group as one terminal
substituent group, it is preferable that the other terminal
substituent group does not include a ring structure other than a
ring structure included in a cyclic imide group.
[0063] In addition, including at least one ring structure in the
compound is preferable from a viewpoint of improving the surface
hardness of the cellulose acylate film to be obtained. From a
viewpoint of improving hardness, an aspect in which the ring
structure is included in a connecting group existing between the
connecting groups selected from the group described above and an
aspect in which the ring structure exists as a terminal substituent
group are preferable. Furthermore, when the polar group is included
as one terminal substituent group, it is also preferable that the
ring structure is included in the other terminal substituent
group.
[0064] Examples of another preferred aspect include an aspect in
which the connecting group having the ring structure exists between
two connecting groups selected from the group consisting of the
bivalent connecting group denoted by --NH--(C.dbd.O)--O-- and the
bivalent connecting group denoted by --NH--(C--O)--NR--. In such an
aspect, it is preferable that the polar group does not have a ring
structure.
[0065] Alternatively, it is also preferable that the polar group
described above has a ring structure. As described above, a cyclic
imide group is preferable as the polar group having a ring
structure. It is preferable that the cyclic polar group exists as a
terminal substituent group.
[0066] On the other hand, examples of a cyclic group which does not
correspond to the polar group described above are able to
preferably include a cyclic aliphatic group or an aromatic group
having 6 to 30 carbon atoms. A terminal cyclic group which does not
correspond to the polar group described above may be a fused ring,
and is preferably a single ring. Specifically, examples of the
terminal cyclic group include an aliphatic ring (a cyclohexane
ring, and the like), an aromatic carbon ring (a benzene ring, a
naphthalene ring, and the like), a hetero ring (a morpholine ring,
a piperidine ring, a piperazine ring, and the like), and the like,
and the aromatic carbon ring is preferable as the terminal cyclic
group. Specifically, an aryl group having 6 to 30 carbon atoms
(more preferably an aryl group having 6 to 20 carbon atoms, and
more preferably an aryl group having 6 to 10 carbon atoms) as the
terminal cyclic group, and a benzene ring is particularly
preferable as the terminal cyclic group. That is, it is preferable
that the terminal cyclic group which does not correspond to the
polar group described above is a phenyl group. The phenyl group may
be substituted or may not be substituted, and a non-substitutional
phenyl group is preferable.
[0067] Furthermore, examples of a cyclic group which does not
correspond to the polar group described above are able to include a
cyclic group (a nitrogen-containing heterocyclic group) formed
along with the substituent group represented by R of the bivalent
connecting group denoted by --NH--(C.dbd.O)--NR--. A
nitrogen-containing 6-membered heterocyclic group is preferable as
the nitrogen-containing heterocyclic group formed as described
above, and a morpholino group is more preferable as the
nitrogen-containing heterocyclic group formed as described above.
The nitrogen-containing heterocyclic group may have a substituent
group, or may be a non-substitutional group. It is preferable that
the nitrogen-containing heterocyclic group is a non-substitutional
nitrogen-containing heterocyclic group. Examples of a substituent
group which is substituted for the nitrogen-containing heterocyclic
group are able to include the substituent groups exemplified in the
group of substituent groups T described above.
[0068] On the other hand, the ring structure included in the
connecting group is identical to that described in Z.sup.1 of
Formula A-1 described below.
[0069] In JP2005-272566A described above, an additive for improving
retardation (Rth) in a thickness direction of the film is
disclosed, but when the film is thinned, whitening of the film due
to volatilization is likely to occur. Therefore, it is preferable
that the compound used as an additive for a cellulose acylate film
has low volatility from a viewpoint of providing a cellulose
acylate film having high transparency. In this regard, in one
aspect, the compound is able to exhibit low volatility. From a
viewpoint of further reducing the volatilization, the molecular
weight of the compound is preferably greater than or equal to 230,
is more preferably greater than or equal to 250, is even more
preferably greater than or equal to 300, and is still more
preferably greater than or equal to 350. In addition, it is
preferable that two or more types of compounds having different
structures are mixed into the cellulose acylate film. In one
aspect, mixing two or more types of compounds is preferable from a
viewpoint of reducing the volatility. On the other hand, in order
to prevent an increase in haze, it is preferable that a compound
having excellent compatibility with respect to the cellulose
acylate is used as the additive for a cellulose acylate film. From
this viewpoint, the molecular weight of the compound is preferably
less than or equal to 2000, and is more preferably less than or
equal to 1500.
[0070] Furthermore, when the compound is a multimer, the molecular
weight indicates a weight average molecular weight. In the present
invention, the average molecular weight indicates an average
molecular weight measured by gel permeation chromatography (GPC) in
terms of polystyrene. Examples of specific measurement conditions
are able to include the following measurement conditions. An
average molecular weight in the following example is a value
measured in the following measurement conditions.
[0071] GPC Device: HLC-8320 (manufactured by Tosoh
Corporation):
[0072] Column: Using TSK gel Super HZM-H, TSK gel Super HZ4000, and
TSK gel Super HZ2000 together, (manufactured by Tosoh Corporation,
4.6 mmID (an inner diameter).times.15.0 cm)
[0073] Eluant: Tetrahydrofuran (THF)
[0074] A preferred aspect of the compound described above is a
compound denoted by Formula A described below.
Q.sup.A-L.sup.1-X--C(--O)--NH-L.sup.2Q.sup.B Formula A
[0075] In Formula A, X represents --O-- or --NR--, and R represents
a hydrogen atom or a substituent group. L.sup.1 and L.sup.2 each
independently represents a single bond, or any one of an alkylene
group, an arylene group, --O--, --NR.sup.1--, --S--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
types thereof. R.sup.1 represents a hydrogen atom or a substituent
group. Q.sup.A and Q.sup.B each independently represent a
substituent group, and at least one of Q.sup.A and Q.sup.B
represents the polar group described above or the terminal group
included in the substituent group described above. When X
represents --NR--, L.sup.1 represents a single bond, and Q.sup.A
has a ring structure, the ring structure included in Q.sup.A may be
a ring structure formed along with R of --NR--.
[0076] In Formula A, X represents --O-- or --NR--. R represents a
hydrogen atom or a substituent group, and examples of the
substituent group include the substituent groups selected from the
group of substituent groups T described above. Among them, an alkyl
group and an aryl group which may be substituted are preferable as
the substituent group, and an alkyl group substituted with a cyano
group which is a polar group is more preferable as the substituent
group. In Formula A, the connecting group selected from the group
described above, specifically, may include one or more bivalent
connecting groups denoted by --NH--C(.dbd.O)--O--, --O--C(O)--NH--,
or --NH--C(--O)--NR--, --NR--C(.dbd.O)--NH--. The number of
connecting groups selected from the group described above is as
described above. In addition, all of the connecting groups selected
from the group described above which exist in the compound may be
identical to each other or different from each other.
[0077] Q.sup.A and Q.sup.B each independently represent a
substituent group, and at least one of Q.sup.A and Q.sup.B
represents the polar group described above or the terminal group
included in the polar group described above. The details of the
polar group are as described above. In one aspect, when one of
Q.sup.A and Q.sup.B represents the polar group described above or
has the polar group described above, it is preferable that the
other is a substituent group having a ring structure. The details
thereof are as described above.
[0078] L.sup.1 and L.sup.2 each independently represent a single
bond, or any one of an alkylene group, an arylene group, --O--,
--NR.sup.1--, --S--, and --C(.dbd.O)--, or a group formed of a
combination of two or more types thereof. An alkylene group having
1 to 20 carbon atoms is more preferable as the alkylene group
represented by L.sup.1 and L.sup.2 or included in L.sup.1 and
L.sup.2, and an alkylene group having 1 to 15 carbon atoms is more
preferable as the alkylene group represented by L.sup.1 and L.sup.2
or included in L.sup.1 and L.sup.2. The alkylene group may be any
one of a straight-chain alkylene group, a branched alkylene group,
a cyclic alkylene group. Specific examples of the alkylene group
include a methylene group, an ethylene group, a propylene group, a
butylene group, a pentylene group, a hexylene group, a
cyclohexylene group, a 2,2'-methylene bis(cyclohexylene) group, a
hexahydroxylylene group, and the like. The alkylene group may have
a substituent group. Examples of the substituent group which may be
included in the alkylene group include the group of substituent
groups T described below. Among them, an alkyl group, an acyl
group, an aryl group, an alkoxy group, and a carbonyl group are
preferable as the substituent group included in the alkylene group.
In addition, an alkylene group having 1 to 8 carbon atoms is more
preferable as the straight-chain alkylene group or the branched
alkylene group, an alkylene group having 1 to 3 carbon atoms is
even more preferable as the straight-chain alkylene group or the
branched alkylene group, a methylene group, an ethylene group, a
propylene group, and an isopropylene group are still more
preferable as the straight-chain alkylene group or the branched
alkylene group. An alkylene group having 3 to 15 carbon atoms is
more preferable as the cyclic alkylene group, and an alkylene group
having 5 to 10 carbon atoms is even more preferable as the cyclic
alkylene group. A cyclohexylene group having a substituent group is
preferable as the cyclohexylene group, and an alkyl substituted
cyclohexylene group is more preferable as the cyclohexylene group.
An alkyl substituted cyclohexylene group having the following
structure is able to be exemplified as a preferred alkyl
substituted cyclohexylene group. In the following description, *
represents a bonding position with respect to the other structure
configuring the compound denoted by Formula A.
##STR00006##
[0079] In addition, preferred examples of the alkyl substituted
cyclohexylene group are able to include a hexahydroxylylene group
described below.
##STR00007##
[0080] An arylene group having 5 to 20 carbon atoms is preferable
as the arylene group represented by L.sup.1 and L.sup.2 or included
in L.sup.1 and L.sup.2, an arylene group having 5 to 15 carbon
atoms is more preferable as the arylene group represented by
L.sup.1 and L.sup.2 or included in L.sup.1 and L.sup.2, and an
arylene group having 5 to 12 carbon atoms is even more preferable
as the arylene group represented by L.sup.1 and L.sup.2 or included
in L.sup.1 and L.sup.2. Specific examples of the arylene group
include a phenylene group, a xylylene group, a biphenylene group, a
naphthylene group, a 2,2'-methylene bisphenyl group, and the like.
The arylene group may have a substituent group. Examples of the
substituent group which may be included in the arylene group
include a group of substituent groups T described below. Among
them, an alkyl group, an acyl group, an aryl group, an alkoxy
group, and a carbonyl group are preferable as the substituent group
included in the arylene group. More preferred examples of the
arylene group include a xylylene group and a tetramethyl xylylene
group.
[0081] When L.sup.1 and L.sup.2 represent any one of an alkylene
group, an arylene group, --O--, --NR.sup.1--, --S--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
types thereof, it is preferable that L.sup.1 and L.sup.2 represent
any one of an alkylene group, an arylene group, --O--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
types thereof. In addition, in the group represented by L.sup.1 and
L.sup.2, the number of carbon atoms in a main chain portion is
preferably in a range of 1 to 10, and is more preferably in a range
of 1 to 5.
[0082] Specific preferred examples of the group represented by
L.sup.1 and L.sup.2 include an alkylene group, and structures
denoted by Formulas (2A) to (2E) described below.
-{(CR.sup.21R.sup.22).sub.ja--O--(C.dbd.O)}.sub.jb-* Formula
(2A)
-{(CR.sup.21R.sup.22).sub.ja--O}.sub.jb-* Formula (2B)
-{(CR.sup.21R.sup.22).sub.ja--(C.dbd.O)--O-}.sub.jb-* Formula
(2C)
--{(CR.sup.21R.sup.22).sub.ja--NR.sup.1(C.dbd.O)--O}.sub.jb-*
Formula (2D)
-{(CR.sup.21R.sup.22).sub.ja--O--(C.dbd.O)--NR.sup.1-}.sub.jb-*
Formula (2E)
[0083] In Formulas (2A) to (2E), * represents a bonding position
with respect to the substituent group represented by Q.sup.A or
Q.sup.B, R.sup.21 and R.sup.22 each independently represent a
hydrogen atom or an alkyl group having 1 to 3 carbon atoms, ja and
jb each independently represent an integer of greater than or equal
to 1, and is preferably an integer in a range of 1 to 3, and when a
plurality of R.sup.21s and R.sup.22s exist, the plurality of
R.sup.21s and R.sup.22s may be identical to each other or different
from each other, respectively.
[0084] In Formulas (2A) to (2E), when two or more structures
denoted by --(CR.sup.21R.sup.22)-- are included, it is preferable
that all of R.sup.21 and R.sup.22 are hydrogen atoms or at least
one of R.sup.21 and R.sup.22 is an alkyl group.
[0085] R.sup.1 of --NR.sup.1-- represents a hydrogen atom or a
substituent group, examples of the substituent group include an
alkyl group, an alkenyl group, an aryl group, and an acyl group,
and a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
an alkenyl group having 2 to 8 carbon atoms, an alkynyl group
having 2 to 8 carbon atoms, and an aryl group having 6 to 18 carbon
atoms (for example, a group having a benzene ring and a naphthalene
ring) are preferable as the substituent group, and a hydrogen atom
or an alkyl group having 1 to 4 carbon atoms is more preferable as
the substituent group.
[0086] In addition, it is preferable that Q.sup.A is a monovalent
substituent group denoted by Formula (a) described below or a
substituent group in which one or more of this monovalent
substituent groups are bonded to L.sup.1 through a connecting
group.
*-L.sup.1-X.sup.1--C(.dbd.O)--X.sup.2-L.sup.2-Q.sup.B Formula
(a)
[0087] Alternatively, it is preferable that Q.sup.B is a monovalent
substituent group denoted by Formula (b) described below or a
substituent group in which one or more of this monovalent
substituent groups are bonded to L.sup.2 through a connecting
group.
Q.sup.A-L.sup.1-X.sup.1--C(.dbd.O)--X.sup.2-L.sup.2-* Formula
(b)
[0088] In Formulas (a) and (b) described above, * represents a
bonding position with respect to the other structure configuring
the compound denoted by Formula A, Q.sup.A, Q.sup.B, L.sup.1, and
L.sup.2 are identical to those of Formula A, respectively, one of
X.sup.1 and X.sup.2 represents --NH--, the other represents --O--
or --NR--, and R is identical to that of Formula A. Examples of the
connecting group are able to include the connecting groups
described in Z.sup.1 of Formula A-1.
[0089] That is, it is preferable that the compound denoted by
Formula A has two or more structures denoted by
*-L.sup.1-X--C(.dbd.O)--NH-L.sup.2-* in one molecule. In the above
description, * represents a bonding position with respect to the
other structure configuring the compound denoted by Formula A, and
X, L.sup.1, and L.sup.2 are identical to those of Formula A,
respectively.
[0090] As described above, in Formula A, when X represents --NR--,
L.sup.1 represents a single bond, and Q.sup.A has a ring structure,
the ring structure included in Q.sup.A is able to be a ring
structure formed along with R of --NR--. An aspect in which the
compound denoted by Formula A has the ring structure described
above is denoted by Formula A-a described below.
##STR00008##
[0091] In Formula A-a, G represents an atom group forming a ring
structure along with a connecting nitrogen atom, and L.sup.2 and
Q.sup.B are identical to those of Formula A, respectively.
[0092] The ring structure (a nitrogen-containing hetero ring)
formed by G is a substitutional or non-substitutional
nitrogen-containing hetero ring, is preferably a substitutional or
non-substitutional nitrogen-containing 6-membered hetero ring, and
is more preferably a substitutional or non-substitutional
morpholino group. As described above, it is preferable the
nitrogen-containing hetero ring is a non-substitutional
nitrogen-containing hetero ring. An aspect in which the compound
denoted by Formula A has a non-substitutional morpholino group is
denoted by Formula A-a1 described below.
##STR00009##
[0093] In Formula A-a1, L.sup.2 and Q.sup.B are identical to those
of Formula A, respectively.
[0094] The preferred aspects of the compound denoted by Formula A
are able to include a compound denoted by Formula A-1 described
below.
(Q.sup.1-L.sup.1-A-L.sup.21).sub.m-Z.sup.1 Formula A-1
[0095] In Formula A-1, L.sup.11 and L.sup.21 each independently
represent a single bond, or any one of an alkylene group, an
arylene group, --O--, --NR.sup.1--, --S--, and --C(.dbd.O)--, or a
group formed of a combination of two or more types thereof. R.sup.1
represents a hydrogen atom or a substituent group. Q.sup.1
represents a substituent group, Z.sup.1 represents an m-valent
connecting group, A represents a single bond,
*--X--C(.dbd.O)--NH--, or *--NH--C(.dbd.O)--X--, * represents a
bonding position with respect to L.sup.21, X represents --O-- or
--NR--, and R represents a hydrogen atom or a substituent group. m
represents an integer in a range of 2 to 6, a plurality of
Q.sup.1s, As, L.sup.11s, and L.sup.21s may be identical to each
other or different from each other, respectively. Here, at least
one A represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--. In
addition, at least one Q.sup.1 represents the polar group described
above or the terminal group included in the polar group described
above.
[0096] Furthermore, as described in Formula A, when A represents
*--NH--C(.dbd.O)--X--, X represents --NR--, L.sup.11 represents a
single bond, and Q.sup.1 has a ring structure, the ring structure
included in Q.sup.1 may be a ring structure formed along with R of
--NR--.
[0097] L.sup.11 and L.sup.21 are each independently identical to
L.sup.1 and L.sup.2 of Formula A, and the details of a preferred
aspect and the like are identical to those of L.sup.1 and L.sup.2
of Formula A.
[0098] Q.sup.1 represents a substituent group, and preferably,
represents the polar group described above or the terminal group
included in the polar group described above. Preferred polar groups
are as described above.
[0099] In addition, it is preferable that any one of m Q.sup.1s
represents the polar group described above or the terminal group
included in the polar group described above, and in one aspect, it
is preferable that all of m Q.sup.1s represent the polar group
described above, one of m Q.sup.1s represents the polar group
described above and the other represents the terminal group
included in the polar group described above, or all of m Q.sup.1s
represent the terminal group included in the polar group described
above, and it is more preferable that all of the polar groups
included in m Q.sup.1s are the polar groups described above as a
preferred example. In addition, in another aspect, it is preferable
that any one of m Q.sup.1s represents the polar group described
above or the terminal group included in the polar group described
above, and the other Q.sup.1s represent a substituent group having
a ring structure, and it is more preferable that the polar group is
the polar group described above as a preferred examples. The
details of the substituent group having a ring structure are as
described above.
[0100] In addition, when Q.sup.1 represents the terminal group
included in the polar group described above, in one aspect, the
terminal group is preferably an alkyl group.
[0101] In addition, when Q.sup.1 represents the terminal group
included in the polar group described above, it is preferable that
the polar group is configured of the terminal group Q.sup.1 and the
connecting group A selected from the group described above. In this
case, L.sup.11 represents a single bond, and Q.sup.1 and A are
directly connected to each other.
[0102] It is preferable that the compound denoted by Formula A-1
has a ring structure in the molecules. In one aspect, it is
preferable that at least one of Q.sup.1 and Z.sup.1 has a ring
structure, and it is more preferable that at least Z.sup.1 has a
ring structure. The ring structure which is able to be included in
Z.sup.1 will be described below. The ring structure which is able
to be included in Q.sup.1 is as described above. Alternatively, in
another aspect, it is preferable that Q.sup.1 and Z.sup.1 do not
have a ring structure, but any one or both of L.sup.11 and L.sup.21
have a ring structure.
[0103] That is, in Formula A-1, it is preferable that at least one
of L.sup.11, L.sup.21, Q.sup.1, and Z.sup.1 has a ring
structure.
[0104] A represents a single bond, *--X--C(.dbd.O)--NH--, or
*--NH--C(.dbd.O)--X--. Here, at least one of a plurality of As
represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--. X is
identical to X of Formula A. That is, at least one of the plurality
of As represents the connecting group selected from the group
described above. Furthermore, in Formula A-1, m represents an
integer in a range of 2 to 6, and thus a plurality of (m)
constituent units denoted by (Q.sup.1-L.sup.11-A-L.sup.21) exist in
the compound denoted by Formula A-1. In at least one of the
plurality of constituent units denoted by
(Q.sup.1-L.sup.11-A-L.sup.21), when L.sup.21 represents a single
bond and A represents the connecting group selected from the group
described above, the connecting group represented by A is directly
bonded to Z.sup.1. In this case, it is preferable that A represents
*--NH--C(.dbd.O)--X--, and is bonded to Z.sup.1 in a bonding
position *. The details of the connecting group selected from the
group described above are as described above.
[0105] Z.sup.1 represents an m-valent connecting group. m is an
integer in a range of 2 to 6, and thus Z.sup.1 is a bivalent to
hexavalent connecting group. Z.sup.1 is preferably a bivalent to
trivalent connecting group, and is more preferably a bivalent
connecting group. Z.sup.1 is preferably a group including at least
one of a straight-chain aliphatic group, a branched aliphatic
group, or a cyclic aliphatic group and an aromatic group, and is
more preferably a group including at least one of a chain aliphatic
group or a cyclic aliphatic group and an aromatic group.
[0106] Z.sup.1 may be formed of only at least one of the
straight-chain aliphatic group, the branched aliphatic group, or
the cyclic aliphatic group and the aromatic group, or is preferably
a combination of the group and one or more of an oxygen atom and a
straight-chain alkylene group or a branched alkylene group. It is
preferable that the aliphatic group included as Z.sup.1 is a
saturated aliphatic group.
[0107] According to the group including at least one of the
branched or cyclic aliphatic group and the aromatic group, a rigid
structure is obtained, and hardness tends to be improved. The
number of carbon atoms configuring Z.sup.1 is preferably 3 to 20,
and is more preferably 4 to 15.
[0108] Z.sup.1 may have a substituent group, and specific examples
of the substituent group include the group of substituent groups T
described above. When Z.sup.1 includes the cyclic aliphatic group,
it is preferable that the cyclic aliphatic group has a substituent
group. On the other hand, when Z.sup.1 includes the aromatic group,
it is preferable that the aromatic group does not have a
substituent group.
[0109] Specifically, it is preferable that Z.sup.1 is a connecting
group exemplified as follows. Furthermore, * represents a position
at which Z.sup.1 is bonded to L.sup.21 (when L.sup.21 represents a
single bond, Z.sup.1 is directly bonded to A).
##STR00010## ##STR00011##
[0110] In one aspect, it is preferable that Z.sup.1 has a ring
structure, and it is more preferable that Z.sup.1 is a group
including at least one of a cyclic aliphatic group and an aromatic
group. A cyclohexane ring which may have a substituent group and a
benzene ring which may have a substituent group, or a group in
which the cyclohexane ring is bonded to the benzene ring through a
connecting group (preferably an alkylene group having 1 to 3 carbon
atoms) are preferable as the ring structure included in Z.sup.1.
More preferably, the ring structure included in Z.sup.1 is a
cyclohexylene group which may have a substituent group or a
phenylene group which may have a substituent group, or a xylylene
group which may have a substituent group. Even more preferably, the
ring structure included in Z.sup.1 is a cyclohexane ring having one
or more selected from a group consisting of an alkyl group having 1
to 3 carbon atoms, a bivalent connecting group denoted by
--NH--(C.dbd.O)--O--, and a bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- as a substituent group, or a benzene ring
having one or more selected from a group consisting of an alkyl
group having 1 to 3 carbon atoms, a bivalent connecting group
denoted by --NH--(C.dbd.O)--O--, and a bivalent connecting group
denoted by --NH--(C.dbd.O)--NR-- as a substituent group. In such an
aspect, it is preferable that any one or both of both terminal
groups of the compound denoted by Formula A-1 has a ring structure,
and it is also preferable that any one or both of both terminal
groups of the compound denoted by Formula A-1 does not have a ring
structure.
[0111] In addition, in another aspect, Z.sup.1 is preferably a
straight-chain aliphatic group, and is more preferably an alkylene
group, and it is more preferable that Z.sup.1 is an alkylene group,
and at least one of the both terminal groups of the compound
denoted by Formula A-1 does not have a ring structure, and it is
even more preferable that Z.sup.1 is an alkylene group, and any one
of the both terminal groups of the compound denoted by Formula A-1
does not have a ring structure.
[0112] Preferred aspects of the compound denoted by Formula A-1 are
able to include a compound denoted by Formula A-2 described
below.
##STR00012##
[0113] In Formula A-2, Q.sup.2 represents a substituent group,
L.sup.31 and L.sup.41 each independently represent a single bond,
or any one of an alkylene group, an arylene group, --O--,
--NR.sup.1--, --S--, and --C(.dbd.O)-- or a group formed of a
combination of two or more types thereof. R.sup.1 represents a
hydrogen atom or a substituent group. A represents a single bond,
*--X--C(.dbd.O)--NH--, or *--NH--C(.dbd.O)--X--, and * represents a
bonding position with respect to L.sup.41. R.sup.11 represents an
alkyl group having 1 to 3 carbon atoms. a represents an integer in
a range of 0 to 10, and when a is greater than or equal to 1, a
plurality of R.sup.11s may be identical to each other or different
from each other. m1 represents 2 or 3, and a plurality of Q.sup.2s,
L.sup.31s, L.sup.41s, and As may be identical to each other or
different from each other, respectively. Here, at least one A
represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--. At least
one of the plurality of Q.sup.2s represents the polar group
described above or the terminal group included in the polar group
described above. When A represents *--NH--C(.dbd.O)--X--, X
represents --NR--, L.sup.31 represents a single bond, and Q.sup.2
has a ring structure, the ring structure included in Q.sup.2 may be
a ring structure formed along with R of --NR--.
[0114] Q.sup.2 represents a substituent group, and at least one of
the plurality of Q.sup.2s represents the polar group described
above. Q.sup.2 is identical to Q.sup.1 of Formula A-1, and a
preferred range is also identical to that of Q.sup.1 of Formula
A-1.
[0115] L.sup.31 and L.sup.41 are each independently identical to
L.sup.11 and L.sup.21 of Formula A-1, preferred ranges are also
identical to those of L.sup.11 and L.sup.21 of Formula A-1.
[0116] R.sup.11 represents an alkyl group having 1 to 3 carbon
atoms, and examples of R.sup.11 include a methyl group, an ethyl
group, a 1-propyl group, a 2-propyl group, and the like. R.sup.11
is preferably a methyl group.
[0117] m1 represents 2 or 3, and is preferably 2. a represents an
integer of 0 to 10, is preferably 0 to 5, is more preferably 0 to
3, and is even more preferably 1 to 3.
[0118] Specific examples of a bonding position 2 or 3 side chains
in the cyclohexane ring of Formula (A-2) are as follows.
[0119] * described below is a position at which the side chain is
bonded to
##STR00013##
[0120] Preferred aspects of the compound denoted by Formula A-1 are
able to include a compound denoted by Formula (A-3) described
below.
##STR00014##
[0121] In Formula A-3, Q.sup.3 represents a substituent group, and
L.sup.51 and L.sup.61 each independently represent a single bond,
or any one of an alkylene group, --O--, --NR.sup.1--, --S--, and
--C(.dbd.O)--, or a group formed of a combination of two or more
types thereof. R.sup.1 represents a hydrogen atom or a substituent
group. A represents a single bond, *--X--C(.dbd.O)--NH--, or
*--NH--C(.dbd.O)--X--, and * represents a bonding position with
respect to L.sup.61. R.sup.12 represents an alkyl group having 1 to
3 carbon atoms, and b represents an integer in a range of 0 to 5.
When b is an integer of greater than or equal to 1, a plurality of
R.sup.12s may be identical to each other or different from each
other. m2 represents 2 or 3, and a plurality of Q.sup.3s,
L.sup.51s, L.sup.61s, and As may be identical to each other or
different from each other, respectively. Here, at least one of the
plurality of As represents *--X--C(.dbd.O)--NH-- or
*--NH--C(.dbd.O)--X--, and at least one of the plurality of
Q.sup.3s represents the polar group described above or the terminal
group included in the polar group described above.
[0122] Q.sup.3 represents a substituent group, and at least one of
the plurality of Q.sup.3s includes the polar group described above.
Q.sup.3 is identical to Q.sup.1 of Formula A-1, and a preferred
range is also identical to that of Q.sup.1 of Formula A-1.
[0123] L.sup.51 and L.sup.61 are each independently identical to
L.sup.11 and L.sup.21 of Formula A-1, preferred ranges are also
identical to those of L.sup.11 and L.sup.21 of Formula A-1.
[0124] R.sup.12 represents an alkyl group having 1 to 3 carbon
atoms, and examples of the alkyl group include a methyl group, an
ethyl group, a 1-propyl group, a 2-propyl group, and the like.
R.sup.12 is preferably a methyl group.
[0125] m2 represents 2 or 3, and is preferably 2. b represents an
integer of 0 to 5, is more preferably 0 to 3, and is particularly
preferably 0.
[0126] Specific examples of a bonding position of 2 or 3 side
chains in a benzene ring of Formula A-3 are as follows.
[0127] * described below is a position at which the side chain is
bonded to
##STR00015##
[0128] Preferred aspects of the compound denoted by Formula A-2 are
able to include a compound denoted by Formula A-4 described below,
and preferred aspects of the compound denoted by Formula A-3 are
able to include a compound denoted by Formula A-5 described
below.
##STR00016##
[0129] In Formulas A-4 and A-5, L.sup.1a and L.sup.1b each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, and --C(--O)-- or a group formed of
a compound of two or more thereof. X represents --O-- or --NR--,
and R represents a hydrogen atom or a substituent group. A
plurality of Xs may be identical to each other or different from
each other. Q.sup.1a and Q.sup.1b each independently represent a
cyano group, a hydroxyl group, a succinimide group, a
hexahydrophthalimide group, a methoxy carbonyl group, an alkoxy
carbonyl amino group, an alkyl aminocarbonyl oxy group, an alkyl
aminocarbonyl amino group, an alkyl group, a phenyl group, or a
benzyl group, or represents a morpholino group formed along with R
of --NR-- when adjacent L.sup.1a or L.sup.1b represents a single
bond, and X represents --NR--. Here, at least one of Q.sup.1a and
Q.sup.1b represents the polar group described above, or the
terminal group included in the polar group described above.
[0130] L.sup.1a and L.sup.1b each independently represent a single
bond, or any one of an alkylene group, an arylene group, --O--, and
--C(.dbd.O)--, or a group formed of a combination of two or more
thereof. The alkylene group is identical to the alkylene group
described in L.sup.1 and L.sup.2 of Formula A described above. In
addition, in the group represented by L.sup.1a and L.sup.1b, the
number of carbon atoms in a main chain portion is preferably in a
range of 1 to 10, and is more preferably in a range of 1 to 5.
[0131] Q.sup.1a and Q.sup.1b each independently represent a cyano
group, a hydroxyl group, a succinimide group, a
hexahydrophthalimide group, a methoxy carbonyl group, an alkoxy
carbonyl amino group, an alkyl aminocarbonyl oxy group, an alkyl
aminocarbonyl amino group, an alkyl group, a phenyl group, or a
benzyl group, or represent the morpholino group described above.
Here, at least one of Q.sup.1a and Q.sup.1b represents the polar
group described above or the terminal group included in the polar
group described above. Preferred combinations of Q.sup.1a and
Q.sup.1b are able to include combinations described below.
[0132] (Combination 1) Cyano Group and Cyano Group
[0133] (Combination 2) Succinimide Group and Succinimide Group
[0134] (Combination 3) Hexahydrophthalimide Group and
Hexahydrophthalimide Group
[0135] (Combination 4) Cyano Group and Phenyl Group
[0136] (Combination 5) Methoxy Carbonyl Group and Phenyl Group
[0137] (Combination 6) Hydroxyl Group and Hydroxyl Group
[0138] (Combination 7) Morpholino Group and Cyano Group
[0139] (Combination 8) Alkoxy Carbonyl Amino Group and Alkoxy
Carbonyl Amino Group
[0140] (Combination 9) Alkoxy Carbonyl Amino Group and
Aminocarbonyl Oxy Group
[0141] (Combination 10) Alkoxy Carbonyl Amino Group and Alkyl
Group
[0142] (Combination 11) Aminocarbonyl Oxy Group and Alkyl Group
[0143] X is identical to X of Formula A-1, and a preferred range is
also identical to that of X of Formula A-1.
[0144] Examples of the preferred aspect of the compound denoted by
Formula A-4 are able to include a compound denoted by Formula A-6
described below, and examples of the preferred aspect of the
compound denoted by Formula A-5 are able to include a compound
denoted by Formula A-7 described below and a compound denoted by
Formula A-8 described below.
##STR00017##
[0145] In Formula A-6, Q.sup.2a and Q.sup.2b each independently
represent a cyano group, a methoxy carbonyl amino group, an ethoxy
carbonyl amino group, a 1-propoxy carbonyl amino group, a 2-propoxy
carbonyl amino group, a methyl aminocarbonyl oxy group, an ethyl
aminocarbonyl oxy group, a 1-propyl aminocarbonyl oxy group, a
2-propyl aminocarbonyl oxy group, an alkyl group, a phenyl group,
or a benzyl group, and at least one of Q.sup.2a and Q.sup.2b
represents a cyano group, a methoxy carbonyl amino group, an ethoxy
carbonyl amino group, a 1-propoxy carbonyl amino group, a 2-propoxy
carbonyl amino group, a methyl aminocarbonyl oxy group, an ethyl
aminocarbonyl oxy group, a 1-propyl aminocarbonyl oxy group, or a
2-propyl aminocarbonyl oxy group. Preferably, both of Q.sup.2a and
Q.sup.2b represent a cyano group. L.sup.2a and L.sup.2b each
independently represent a single bond, or any one of an alkylene
group, an arylene group, --O--, and --C(.dbd.O)-- or a group formed
of a combination of two or more thereof. X represents --O-- or
--NR.sup.1--, and R.sup.1 represents a hydrogen atom or a
substituent group. A plurality of Xs may be identical to each other
or different from each other.
##STR00018##
[0146] In Formula A-7, any one of Q.sup.3a and Q.sup.3a represents
a cyano group, a succinimide group, or a hexahydrophthalimide
group, and the other represents an alkyl group, a phenyl group, or
a benzyl group.
[0147] In a preferred aspect, any one of Q.sup.3a and Q.sup.3b
represents a cyano group, and the other represents a phenyl
group.
[0148] In addition, in another aspect, it is preferable that in the
compound denoted by Formula A-7, both of Q.sup.3a and Q.sup.3b do
not include a cyano group. For example, when any one of Q.sup.3a
and Q.sup.3b is a cyano group substituted alkyl group, it is
preferable that the other is a succinimide group or a
hexahydrophthalimide group. In addition, when any one of Q.sup.3a
and Q.sup.3b is a cyano group, it is preferable that the other is a
phenyl group or a benzyl group.
[0149] In one aspect, the alkyl group described above is a
non-substitutional alkyl group, and in another aspect, the alkyl
group described above is a substitutional alkyl group. Examples of
the substitutional alkyl group are able to include an aryl carbonyl
alkyl group such as a benzoyl alkyl group, an aryl oxy alkyl group
such as a phenyl oxy alkyl group, and the like.
[0150] L.sup.3a and L.sup.3b each independently represent a single
bond, or any one of an alkylene group, an arylene group, --O--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
thereof. X represents --O-- or --NR--, R represents a hydrogen atom
or a substituent group; and a plurality of Xs may be identical to
each other or different from each other.
##STR00019##
[0151] In Formula A-8, Q.sup.4a and Q.sup.4b each independently
represent a methoxy carbonyl amino group, an ethoxy carbonyl amino
group, a 1-propoxy carbonyl amino group, a 2-propoxy carbonyl amino
group, methyl aminocarbonyl oxy group, an ethyl aminocarbonyl oxy
group, a 1-propyl aminocarbonyl oxy group, a 2-propyl aminocarbonyl
oxy group, alkyl group, a phenyl group, or a benzyl group, and at
least one of Q.sup.4a and Q.sup.4b represents a methoxy carbonyl
amino group, an ethoxy carbonyl amino group, a 1-propoxy carbonyl
amino group, a 2-propoxy carbonyl amino group, a methyl
aminocarbonyl oxy group, an ethyl aminocarbonyl oxy group, a
1-propyl aminocarbonyl oxy group, or a 2-propyl aninocarbonyl oxy
group. L.sup.4a and L.sup.4b each independently represent a single
bond, or any one of an alkylene group, an arylene group, --O--, and
--C(.dbd.O)-- or a group formed of a combination of two or more
thereof. X represents --O-- or --NR--, and R represents a hydrogen
atom or a substituent group. A plurality of Xs may be identical to
each other or different from each other.
[0152] In Formulas A-6, A-7, and A-8, each of L.sup.2a, L.sup.2b,
L.sup.3a, L.sup.3b, L.sup.4a, and L.sup.4b is identical to L.sup.1a
and L.sup.1b of Formulas A-4 and A-5, and preferred ranges are also
identical to those of L.sup.1a and L.sup.1b of Formulas A-4 and
A-5.
[0153] In Formulas A-6, A-7, and A-8, X is identical to X of
Formula A-1, and a preferred range is also identical to X of
Formula A-1.
[0154] In addition, examples of the preferred aspect of the
compound denoted by Formula A-1 are able to include a compound
denoted by Formula A-9 described below.
Q.sup.100-(L.sup.100-A.sup.100)m1-Q.sup.101 Formula A-9:
[0155] In Formula A-9, L.sup.100 represents any one of a single
bond, an alkylene group, and
##STR00020##
and * represents a bonding position with respect to the other
structure configuring the compound denoted by Formula A-9. One or
more of a plurality of L.sup.100s represent a group other than a
single bond. Q.sup.100 and Q.sup.101 each independently represent
an alkyl group, a hydroxyl group, or a cyano group. A.sup.100
represents *--X--C(.dbd.O)--NH-- or *--NH--C(.dbd.O)--X--, and *
represents a bonding position with respect to L.sup.100. X
represents --O-- or --NR--, and R represents a hydrogen atom or a
substituent group. m1 represents an integer in a range of 2 to
6.
[0156] A plurality of L.sup.100s and A.sup.100s may be identical to
each other or different from each other, respectively.
[0157] In Formula A-9, the alkylene group represented by L.sup.100
is identical to the alkylene group represented by L.sup.1 and
L.sup.2 of Formula A described above.
[0158] In Formula A-9, the alkyl group represented by Q.sup.100 and
Q.sup.101 is an alkyl group having 1 to 3 carbon atoms.
[0159] In Formula A-9, X is identical to X of Formula A-1, and a
preferred range is also identical to that of X of Formula A-1.
[0160] In the compound described above, the equivalent weight U
obtained as U=[(Molecular Weight)/(Number of Connecting Groups
Included in One Molecule, Which Are Selected from Group Consisting
of Bivalent Connecting Group Denoted by NH--(C.dbd.O)--O-- and
Bivalent Connecting Group Denoted by --NH--(C.dbd.O)--NR-- in Which
R Represents Hydrogen Atom or Substituent Group)] is less than or
equal to 515. A preferred range of the equivalent weight U is as
described above.
[0161] Hereinafter, in the compound described above, the compound
which is preferably used in the present invention is exemplified,
but the present invention is not limited thereto.
##STR00021## ##STR00022## ##STR00023##
TABLE-US-00001 TABLE 1 ##STR00024## Composition Number A B 2-1-A
*--OCH.sub.2CH.sub.2OPh *--N(CH.sub.3)CH.sub.2COOCH.sub.3 2-2-A
*--OCH.sub.2CH.sub.2OPh *--N(CH.sub.2CH.sub.2CN).sub.2 2-3-A
*--OCH.sub.2CH.sub.2OPh *--N(CH.sub.2CN).sub.2 2-4-A
*--OCH.sub.2CH.sub.2CN *--N(CH.sub.2CH.sub.2CN).sub.2 2-5-A
*--OCH.sub.2CH.sub.2CN *--N(CH.sub.2CN).sub.2 2-6-A
*--OCH.sub.2CH.sub.2OPh *--OCH.sub.2CH.sub.2CN 2-1-B
*--N(CH.sub.3)CH.sub.2COOCH.sub.3 *--OCH.sub.2CH.sub.2OPh 2-2-B
*--N(CH.sub.2CH.sub.2CN).sub.2 *--OCH.sub.2CH.sub.2OPh 2-3-B
*--N(CH.sub.2CN).sub.2 *--OCH.sub.2CH.sub.2OPh 2-4-B
*--N(CH.sub.2CH.sub.2CN).sub.2 *--OCH.sub.2CH.sub.2CN 2-5-B
*--N(CH.sub.2CN).sub.2 *--OCH.sub.2CH.sub.2CN 2-6-B
*--OCH.sub.2CH.sub.2CN *--OCH.sub.2CH.sub.2OPh In Table, Ph: Phenyl
Group, and *Bonding Position)
##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
##STR00030##
[0162] (In exemplary compounds 6-1 to 6-6, --C.sub.3H.sub.6-- is
--CH(CH.sub.3)--CH.sub.2-- or --CH.sub.2--CH(CH.sub.3)--.)
[0163] The compound described above is able to be manufactured by a
known method. For example, the compound described above is able to
be obtained by an addition reaction, or the like, of alcohol or
amine to alkyl or aryl isocyanate.
[0164] It is preferable that a catalyst is used at the time of
performing the addition reaction of alcohol or amine to alkyl or
aryl isocyanate, and a known urethanized catalyst of the related
art such as amines, a salt of a metal organic acid or a metal
chelate compound of zinc, tin, and the like, and an organic metal
compound of zinc, tin, bismuth are able to be used as the
catalyst.
[0165] For example, dibutyl tin dilaurate, dibutyl tin diacetate,
and the like are preferably used as the urethanized catalyst.
[0166] Furthermore, when a component for introducing a bivalent
connecting group denoted by --NH--(C.dbd.O)--O-- and a component
for introducing a bivalent connecting group denoted by
--NH--(C.dbd.O)--NR-- are used together at the time of synthesizing
the compound described above, a structure including only one of the
two connecting groups (a so-called symmetric structure) and a
structure including both of the two connecting groups (a so-called
asymmetric structure) are able to be obtained. In addition, a
mixture of compounds each having different number of connecting
groups described above to be included is able to be obtained as the
asymmetric structure. In the present invention, the compound is
able to be used for manufacturing a cellulose acylate film in a
state of a mixture of the compound having a symmetric structure and
a compound having an asymmetric structure or in a state of a
mixture of the compounds each having different number of connecting
groups described above to be included. Alternatively, a compound
having a desired structure is able to be purified from the mixture
by a known method, and is able to be used as a single item.
[0167] Any one of a combination of polyvalent isocyanate
(diisocyanate, triisocyanate, and the like) and monohydric alcohol,
a combination of polyhydric alcohol and monovalent isocyanate, a
combination of polyvalent isocyanate (diisocyanate, triisocyanate,
and the like) and monovalent amine, a combination of polyvalent
amine and monovalent isocyanate, and a combination of aminoalcohol
and monovalent isocyanate is able to be preferably used for
synthesizing the compound described above.
[0168] Examples of a polyvalent isocyanate component include
aliphatic diisocyanate such as ethylene diisocyanate, trimethylene
diisocyanate, tetramethylene diisocyanate, hexamethylene
diisocyanate, and isophorone diisocyanate, aromatic diisocyanate
such as p-phenylene diisocyanate, tolylene diisocyanate,
p,p'-diphenyl methane diisocyanate, and 1,5-naphthylene
diisocyanate, m-xylylene diisocyanate, and the like, but the
present invention is not limited thereto. Among them, from
viewpoint of suppressing photo-coloration, the aliphatic
diisocyanate and the m-xylylene diisocyanate in which a conjugated
system is cut are preferable.
[0169] Examples of a monovalent isocyanate component include phenyl
isocyanate, benzyl isocyanate, butyl isocyanate, and the like, but
the present invention is not limited thereto.
[0170] Examples of the polyhydric alcohol are able to include
ethylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, 1,2-propane diol, 1,3-propane diol,
dipropylene glycol, tripropylene glycol, 1,3-butane diol,
1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, trimethylol
propane, trimethylol ethane, glycerin, and the like.
[0171] Examples of the monohydric alcohol include cyano ethanol,
2-hydroxyl ethyl succinimide, 2-hydroxyl ethyl phthalimide, and the
like. In addition, an alcohol component having an aromatic ring is
preferable as an alcohol component, and examples of the alcohol
component having an aromatic ring include benzyl alcohol, phenethyl
alcohol, phenoxy ethanol, and the like.
[0172] Examples of the polyvalent amine are able to include
ethylene diamine, xylylene diamine, 4,4'-diaminodiphenyl methane,
and the like.
[0173] Examples of the monovalent amine include imino
diacetonitrile, imino dipropionitrile, glycine, N-methyl glycine,
and the like. In addition, benzyl amine, cyclohexyl amine,
morpholine, piperidine, and the like are able to be used as the
monovalent amine.
[0174] Examples of the aminoalcohol include 2-aminoethanol,
1-amino-2-propanol, and the like.
[0175] The degree of hydrophilicity of the entire compound
described above is able to be denoted by a C log P value. C log P
is as described above. C log P of the compound described above is
preferably -1.0 to 12.0, is more preferably 0.0 to 10.0, and is
even more preferably 1.0 to 8.0.
[0176] In addition, the melting point of the compound described
above is preferably -50.degree. C. to 250.degree. C., and is more
preferably -30.degree. C. to 200.degree. C. According to such a
range, the effects of the present invention tend to be more
effectively expressed.
[0177] A measurement method of the melting point is not
particularly limited, but is able to be suitably selected from
known methods, and examples of the measurement method include a
measurement method using a trace melting point measure device and
the like.
[0178] (Cellulose Acylate)
[0179] A degree of substitution of the cellulose acylate indicates
a ratio in which three hydroxyl groups existing in a constituent
unit of cellulose (glucose having a (.beta.)1,4-glycoside bond) are
acylated. The degree of substitution (a degree of acylation) is
able to be calculated by measuring the amount of bonded fatty acid
per constituent unit mass of cellulose. In the present invention, a
degree of substitution of a cellulose body is able to be calculated
by dissolving the cellulose body in a solvent such as dimethyl
sulfoxide which is subjected to deuterium substitution, by
measuring a .sup.13C-NMR spectrum, and by obtaining the degree of
substitution from a peak intensity ratio of carbonyl carbon in an
acyl group. A residual hydroxyl group of the cellulose acylate is
able to be substituted with other acyl groups which are different
from the acyl group of the cellulose acylate itself, and then the
degree of substitution is able to be obtained by .sup.13C-NMR
measurement. The details of a measurement method are disclosed in
(Carbohydrate. Res., 273 (1995) 83-91) of TEZUKA et al.
[0180] The degree of substitution of the cellulose acylate used in
the present invention is preferably greater than or equal to 1.5
and less than or equal to 3.0, is more preferably 2.00 to 2.97, is
even more preferably greater than or equal to 2.50 and less than
2.97, and is particularly preferably 2.70 to 2.95.
[0181] In addition, in cellulose acetate using only an acetyl group
as the acyl group of the cellulose acylate, the degree of
substitution is preferably greater than or equal to 2.0 and less
than or equal to 3.0, is more preferably 2.3 to 3.0, is even more
preferably 2.60 to 3.0, is still more preferably 2.6 to 2.97, and
is particularly preferably 2.70 to 2.95, from a viewpoint of a
great surface hardness enhancement effect due to the compound
described above.
[0182] An acetyl group, a propionyl group, and a butyryl group are
particularly preferable, and the acetyl group is more particularly
preferable as the acyl group of the cellulose acylate which is able
to be used in the present invention.
[0183] In the present invention, mixed fatty acid ester formed of
two or more types of acyl groups is also able to be preferably used
as the cellulose acylate. Even in this case, an acetyl group and an
acyl group having 3 to 4 carbon atoms are preferable as the acyl
group. In addition, when the mixed fatty acid ester is used, the
degree of substitution at the time of including the acetyl group as
the acyl group is preferably less than 2.5, and is more preferably
less than 1.9. On the other hand, the degree of substitution at the
time of including the acyl group having 3 to 4 carbon atoms is
preferably 0.1 to 1.5, is more preferably 0.2 to 1.2, and is
particularly preferably 0.5 to 1.1.
[0184] In the present invention, two types of cellulose acylates
having different substituent groups and/or degrees of substitution
may be used together or may be used by being mixed, and a film
formed of a plurality of layers consisting of different cellulose
acylates may be formed by a cocasting method or the like described
below.
[0185] Further, mixed acid ester having a fatty acid acyl group and
a substitutional aromatic acyl group or a non-substitutional
aromatic acyl group disclosed in paragraphs 0023 to 0038 of
JP2008-20896A is also able to be preferably used in the present
invention.
[0186] It is preferable that the cellulose acylate used in the
present invention has a mass average degree of polymerization of
250 to 800, and it is more preferable that the cellulose acylate
used in the present invention has a mass average degree of
polymerization of 300 to 600. In addition, it is preferable that
the cellulose acylate used in the present invention has a number
average molecular weight of 40000 to 230000, it is more preferable
that the cellulose acylate used in the present invention has a
number average molecular weight of 60000 to 230000, and it is most
preferable that the cellulose acylate used in the present invention
has a number average molecular weight of 75000 to 200000.
[0187] The cellulose acylate used in the present invention is able
to be synthesized by using an acid anhydride or an acid chloride as
an acylation agent. When the acylation agent is the acid anhydride,
an organic acid (for example, an acetic acid) or methylene chloride
is used as a reaction solvent. In addition, a protonic catalyst
such as a sulfuric acid is able to be used as a catalyst. When the
acylation agent is the acid chloride, a basic compound is able to
be used as a catalyst. In the most general industrial synthesis
method, cellulose is esterified by a mixed organic acid component
including an organic acid (an acetic acid, a propionic acid, and a
butyric acid) corresponding to an acetyl group and other acyl
groups or an acid anhydride thereof (acetic anhydride, propionic
anhydride, and butyric anhydride), and thus cellulose acylate is
synthesized.
[0188] In the method described above, in general, cellulose such as
cotton linter or wood pulp is subjected to an activation treatment
by an organic acid such as an acetic acid, and then is esterified
by using a mixed liquid of the organic acid component as described
above in the presence of a sulfuric acid catalyst. In general, an
excessive amount of organic acid anhydride component is used with
respect to the amount of hydroxyl group in the cellulose. In this
esterification treatment, a hydrolysis reaction (a depolymerization
reaction) of a cellulose main chain (a (.beta.)1,4-glycoside bond)
progresses in addition to an esterification reaction. When the
hydrolysis reaction of the main chain progresses, the degree of
polymerization of the cellulose acylate decreases, and physical
properties of a cellulose acylate film to be manufactured,
decrease. For this reason, it is preferable that reaction
conditions such as a reaction temperature are determined in
consideration of the degree of polymerization or the molecular
weight of cellulose acylate to be obtained.
[0189] Added Amount
[0190] The added amount of the compound denoted by Formula A is not
particularly limited, but is preferably 1 part by mass to 50 parts
by mass, is more preferably 2 parts by mass to 30 parts by mass, is
even more preferably 2 parts by mass to 20 parts by mass, and is
particularly preferably 4 parts by mass to 15 parts by mass, with
respect to 100 parts by mass of cellulose acylate. Furthermore, two
or more types of compounds described above may be added. Even when
two or more types of compounds are added, a specific example and a
preferred range of the added amount are as described above.
[0191] The cellulose acylate film of the present invention may
contain other additives in addition to the cellulose acylate and
the compound described above. A known plasticizer, an organic acid,
a dye, a polymer, a retardation adjusting agent, a ultraviolet
absorbent, an antioxidant, a matting agent, and the like are
exemplified as the additives. The additives are able to refer to
additives disclosed in paragraphs 0062 to 0097 of JP2012-155287A,
and the contents are incorporated herein. The total blended amount
of the additives is preferably less than or equal to 50 mass %, and
is more preferably less than or equal to 30 mass %, with respect to
cellulose acylate.
[0192] <Manufacturing Method of Cellulose Acylate Film>
[0193] A manufacturing method of the cellulose acylate film of the
present invention is not particularly limited, but it is preferable
that the cellulose acylate film of the present invention is
manufactured by a melting film formation method or a solution film
formation method (a solvent casting method), and it is more
preferable that the cellulose acylate film of the present invention
is manufactured by a solution film formation method (a solvent
casting method). A manufacturing example of a cellulose acylate
film using the solvent casting method is able to refer to each
specification of U.S. Pat. No. 2,336,310A, U.S. Pat. No.
2,367,603A, U.S. Pat. No. 2,492,078A, U.S. Pat. No. 2,492,977A,
U.S. Pat. No. 2,492,978A, U.S. Pat. No. 2,607,704A, U.S. Pat. No.
2,739,069A, and U.S. Pat. No. 2,739,070A, each specification of
GB640731A and GB736892A, and each publication of JP1970-4554B
(JP-S45-4554B), JP1974-5614B (JP-S49-5614B), JP1985-176834A
(JP-S60-176834A), JP1985-203430A (JP-S60-203430A), JP1987-115035A
(JP-S62-115035A), and the like. In addition, the cellulose acylate
film may be subjected to a stretching treatment. A method and
conditions of the stretching treatment, for example, are able to
refer to each publication of JP1987-115035A (JP-S62-115035A),
JP1992-152125A (JP-H04-152125A), JP1992-284211A (JP-H04-284211A),
JP 1992-298310A (JP-H04-29831 OA), JP1999-48271 A (JP-H11-48271A),
and the like.
[0194] (Casting Method)
[0195] Examples of the solution casting method include a method in
which a prepared dope is homogeneously extruded onto a metal
support body from a pressure die, a doctor blade method in which
the film thickness of a dope which has been casted on a metal
support body is adjusted by using a blade, a reverse roll coater
method in which the film thickness is adjusted by using a reversely
rotating roll, and the like, and the pressure die method is
preferable. A coat hanger type die, a T die type die, or the like
is used as the pressure die, and all of the dies are able to be
preferably used. In addition, a cellulose acylate solution is able
to be casted by using various methods which have been known from
the related art in which a cellulose acylate solution is casted and
a film is formed in addition to the methods described herein, and
each condition is set in consideration of a difference in a boiling
point of a solvent to be used, or the like.
[0196] Cocasting
[0197] In the formation of the cellulose acylate film, a lamination
casting method such as a cocasting method, a sequentially casting
method, and a coating method is preferably used, and a concurrently
cocasting method is particularly preferably used from a viewpoint
of stable manufacturing and a reduction in production costs.
[0198] When the cellulose acylate film is manufactured by using the
cocasting method and the sequentially casting method, first, the
cellulose acetate solution (the dope) for each layer is prepared.
The cocasting method (multi-layer concurrently casting) is a
casting method in which the dope is extruded from a die for casting
concurrently extruding a dope for casting of each of the layers
(three layers or three or more layers may be used) from a separate
slit or the like onto a support body for casting (a band or a
drum), the respective layers are concurrently casted, are peeled
off from the support body at a suitable timing, and are dried, and
thus a film is molded. It is possible to concurrently extrude and
cast a dope for a surface layer and a dope for a core layer on the
support for casting in three layers by using an extrusion cocasting
die.
[0199] The sequentially casting method is a casting method in
which, first, a dope for casting of a first layer is extruded from
the die for casting onto the support body for casting, is casted,
and is dried or is not dried, and a dope for casting of a second
layer is extruded from the die for casting of the second layer and
is casted, and in this manner, as necessary, dopes for third or
more layers are sequentially casted and laminated, and then the
dopes are peeled off from the support body at a suitable timing and
are dried, and thus a cellulose acylate film is molded. In general,
the coating method is a method in which a core layer is molded into
the shape of a film by using a solution film formation method, a
coating liquid applied onto a surface layer is prepared, the
coating liquid is applied onto each one surface or is concurrently
applied onto both surfaces of the core layer and is dried by using
a suitable coating machine, and thus a cellulose acylate film
having a laminated structure is molded.
[0200] The compound described above is contained in one or more of
the layers or in all of the layers, and thus it is possible to
obtain a cellulose acylate film having high surface hardness.
[0201] (Stretching Treatment)
[0202] It is preferable that the manufacturing method of the
cellulose acylate film includes a step of stretching after forming.
It is preferable that a stretching direction of the cellulose
acylate film is either a cellulose acylate film transport direction
(an MD direction) or a direction orthogonal to the transport
direction (a TD direction), and it is particularly preferable that
the cellulose acylate film is stretched in the direction orthogonal
to the cellulose acylate film transport direction (the TD
direction) from a viewpoint of a machining process of a polarizing
plate using the cellulose acylate film, which follows after the
stretching.
[0203] A method of stretching the film in the TD direction, for
example, is disclosed in each publication of JP1987-115035A
(JP-S62-115035A), JP1992-152125A (JP-H04-152125A), JP1992-284211A
(JP-H04-284211A), JP1992-298310A (JP-H04-298310A), JP1999-48271A
(JP-H11-48271A), and the like. In a case where the film is
stretched in the MD direction, for example, when the speed of a
transportation roller of the cellulose acylate film is adjusted,
and thus the winding speed of the cellulose acylate film is faster
than the peeling speed of the cellulose acylate film, the cellulose
acylate film is stretched. In a case where the film is stretched in
the TD direction, the cellulose acylate film is able to be
stretched by transporting the cellulose acylate film while holding
the width of the cellulose acylate film with a tenter, and by
gradually widening the width of the tenter. It is also possible to
stretch the cellulose acylate film by using a stretching machine
(preferably monoaxial stretching using a long stretching machine)
after drying the cellulose acylate film.
[0204] When the cellulose acylate film is used as a protective film
of a polarizer, light leakage is suppressed when a polarizing plate
is obliquely viewed, and thus it is necessary that a transmission
axis of the polarizer and an in-plane slow axis of the cellulose
acylate film are arranged to be parallel to each other. In general,
a transmission axis of a roll film-like polarizer which is
continuously manufactured is parallel to a width direction of the
roll film, and thus in order to continuously bond the protective
film which is formed of the roll film-like polarizer described
above and a roll film-like cellulose acylate film, it is necessary
that an in-plane slow axis of the roll film-like protective film is
parallel to a width direction of the cellulose acylate film.
Accordingly, it is more preferable that the stretching is more
frequently performed in the TD direction. In addition, the
stretching treatment may be performed during a film forming step,
or a raw fabric which is formed and is wound may be subjected to
the stretching treatment.
[0205] The stretching in the TD direction is preferably stretching
of 5% to 100%, is more preferably stretching of 5% to 80%, and is
particularly preferably stretching of 5% to 40%. Furthermore,
non-stretching indicates that the stretching is 0%. The stretching
treatment may be performed during the film forming step, or a raw
fabric which is formed and is wound may be subjected to the
stretching treatment. In the former case, the stretching may be
performed in a state of including a residual solvent, and the
stretching is able to be preferably performed when Amount of
Residual Solvent=(Residual Volatile Component Mass/Film Mass after
Heating Treatment).times.100% is 0.05% to 50%. It is particularly
preferable that stretching of 5% to 80% is performed in a state
where the amount of residual solvent is 0.05% to 5%.
[0206] The cellulose acylate film containing the compound described
above is subjected to the stretching treatment, and thus it is
possible to further increase the surface hardness of the film.
[0207] <Physical Properties of Cellulose Acylate Film>
[0208] Surface Hardness:
[0209] The cellulose acylate film of the present invention contains
the compound described above, and thus is able to have high surface
hardness. The surface hardness of the cellulose acylate film is
able to be adjusted by the type or the content of the compound
denoted by Formula A. Knoop hardness is able to be used as an index
of the surface hardness of the cellulose acylate film. The Knoop
hardness is able to be measured by a method described below in
examples.
[0210] Modulus of Elasticity:
[0211] The cellulose acylate film exhibits practically sufficient
modulus of elasticity. The range of the modulus of elasticity is
not particularly limited, but is preferably 1.0 GPa to 6.0 GPa, and
is more preferably 2.0 GPa to 5.0 GPa from a viewpoint of
manufacturing suitability and handling properties. The compound
described above is added into the cellulose acylate film, and thus
the cellulose acylate film is hydrophobized and the modulus of
elasticity is improved, and these properties are advantages of the
present invention.
[0212] Photoelastic Coefficient:
[0213] The absolute value of a photoelastic coefficient of the
cellulose acylate film is preferably less than or equal to
8.0.times.10.sup.-12 m.sup.2/N, is more preferably less than or
equal to 6.times.10.sup.-12 m.sup.2/N, and is even more preferably
less than or equal to 5.times.10.sup.-12 m.sup.2/N. The
photoelastic coefficient of the cellulose acylate film decreases,
and thus when the cellulose acylate film of the present invention
is incorporated in a liquid-crystal display device as a polarizing
plate protective film, it is possible to suppress the occurrence of
unevenness under high temperature and high humidity. The
photoelastic coefficient, unless otherwise specifically stated, is
calculated by being measured according to the following
methods.
[0214] The lower limit value of modulus of photoelasticity is not
particularly limited, and it is practical that the lower limit
value of modulus of photoelasticity is greater than or equal to
0.1.times.10.sup.-12 m.sup.2/N.
[0215] The cellulose acylate film is cut to have a size of 3.5
cm.times.12 cm, and the photoelastic coefficient is measured by
being calculated from a slope of a straight line of a change in Re
corresponding to a stress by measuring Re with an ellipsometer
(M150, manufactured by Jasco Corporation) at each load of no load,
250 g, 500 g, 1000 g, and 1500 g.
[0216] Moisture Content:
[0217] The moisture content of the cellulose acylate film is able
to be evaluated by measuring an equilibrium moisture content at a
constant temperature and humidity. The equilibrium moisture content
is calculated by measuring the moisture amount of a sample which
reaches equilibrium after being placed for 24 hours at the
temperature and humidity described above using a Karl Fischer
method, and by dividing a moisture amount (g) by a sample mass
(g).
[0218] The moisture content of the cellulose acylate film at a
temperature of 25.degree. C. and relative humidity of 80% is
preferably less than or equal to 5 mass %, is more preferably less
than or equal to 4 mass %, and is even more preferably less than 3
mass %. The moisture content of the cellulose acylate film
decreases, and thus when the cellulose acylate film of the present
invention is incorporated in the liquid-crystal display device as
the polarizing plate protective film, it is possible to suppress
the occurrence of display unevenness of the liquid-crystal display
device under high temperature and high humidity. The lower limit
value of the moisture content is not particularly limited, and it
is practical that the lower limit value of the moisture content is
greater than or equal to 0.1 mass %.
[0219] Moisture Permeability:
[0220] The moisture permeability of the cellulose acylate film is
able to be evaluated by measuring the mass of water vapor per 24
hours passing through the sample in an atmosphere of a temperature
of 40.degree. C. and relative humidity of 90% on the basis of a
moisture permeability test (a cup method) of JIS Z0208, and by
converting the mass of the water vapor per 24 hours into the mass
of the water vapor passing through for 24 hours per a sample area 1
m.sup.2.
[0221] The moisture permeability of the cellulose acylate film is
preferably 500 g/m.sup.2day to 2000 g/m.sup.2day, is more
preferably 900 g/m.sup.2day to 1300 g/m.sup.2day, and is
particularly preferably 1000 g/m.sup.2day to 1200 g/m.sup.2day.
[0222] Haze:
[0223] The haze of the cellulose acylate film is preferably less
than or equal to 1%, is more preferably less than or equal to 0.7%,
and is particularly preferably less than or equal to 0.5%. By
setting the haze to be less than or equal to the upper limit value
described above, advantages such as a further increase in
transparency of the cellulose acylate film and ease of use as an
optical film are obtained. The haze, unless otherwise specifically
stated, is calculated by being measured according to the following
methods. The lower limit value of the haze is not particularly
limited, and it is practical that the lower limit value of the haze
is greater than or equal to 0.001%.
[0224] The haze of a cellulose acylate film of 40 mm.times.80 mm is
measured under an environment of a temperature of 25.degree. C. and
relative humidity of 60% by using a hazemeter (HGM-2DP,
manufactured by Suga test Instruments Co., Ltd.) according to JIS
K7136.
[0225] Film Thickness:
[0226] The average film thickness of the cellulose acylate film is
able to be suitably set according to application, and for example,
is 10 m to 100 .mu.m. The average film thickness of the cellulose
acylate film is preferably greater than or equal to 15 .mu.m, and
is more preferably greater than or equal to 20 .mu.m, from a
viewpoint of improving handling properties at the time of preparing
a web-like film. In addition, the average film thickness of the
cellulose acylate film is preferably less than or equal to 100
.mu.m, is more preferably less than or equal to 80 .mu.m, and is
even more preferably less than or equal to 70 .mu.m, from a
viewpoint of easily dealing with a humidity change and of easily
maintaining optical properties.
[0227] In addition, when the cellulose acylate film has a laminated
structure of three or more layers, the film thickness of the core
layer is preferably 3 .mu.m to 70 .mu.m, and is more preferably 5
.mu.m to 60 .mu.m, and the film thickness of a skin layer A and a
skin layer B is preferably 0.5 .mu.m to 20 .mu.m, is particularly
preferably 0.5 .mu.m to 10 .mu.m, and is most preferably 0.5 .mu.m
to 3 .mu.m. The core layer indicates a layer positioned in the
center portion in the three-layer structure, and the skin layer
indicates a layer positioned on an outer side in the three-layer
structure.
[0228] Width:
[0229] The width of the cellulose acylate film is preferably 700 mm
to 3000 mm, is more preferably 1000 mm to 2800 mm, and is
particularly preferably 1300 mm to 2500 mm.
[0230] (Saponification Treatment)
[0231] The cellulose acylate film is able to be used as the
polarizing plate protective film by applying adhesiveness with
respect to the material of the polarizer such as polyvinyl alcohol
through an alkali saponification treatment.
[0232] A method disclosed in paragraph 0211 and paragraph 0212 of
JP2007-86748A is able to be used as a saponification method.
[0233] For example, it is preferable that the alkali saponification
treatment with respect to the cellulose acylate film is performed
in a cycle where the film surface is dipped in an alkali solution,
and then is neutralized with an acidic solution, and is washed with
water and dried. Examples of the alkali solution described above
include a potassium hydroxide solution and sodium hydroxide
solution, and the concentration of hydroxide ions is preferably in
a range of 0.1 mol/L to 5.0 mol/L, and is more preferably in a
range of 0.5 mol/L to 4.0 mol/L. An alkali solution temperature is
preferably in a range of room temperature to 90.degree. C., and is
more preferably in a range of 40.degree. C. to 70.degree. C.
[0234] Easy adhesion processing as disclosed in JP1994-94915A
(JP-H06-94915A) and JP1994-118232A (JP-H06-118232A) may be
performed instead of the alkali saponification treatment.
[0235] [Polarizing Plate]
[0236] A polarizing plate of the present invention includes the
cellulose acylate film described above, and a polarizer.
[0237] In one aspect, the cellulose acylate film of the present
invention is included in a polarizing plate as a protective film.
The polarizing plate according to this aspect includes a polarizer,
and two polarizing plate protective films (transparent films)
protecting both surfaces of the polarizer, and includes the
cellulose acylate film of the present invention as at least one
polarizing plate protective film.
[0238] The cellulose acylate film of the present invention, in
particular, is preferably used as a protective film on a visible
side of an upper side polarizing plate 10. FIG. 1 is an example
illustrating one aspect of a positional relationship between the
polarizing plate of the present invention and a liquid-crystal
display device, in which "1" indicates the cellulose acylate film
of the present invention, "2" indicates the polarizer, "3"
indicates a retardation film, and "4" indicates a liquid-crystal
cell, respectively. In addition, an upper side of FIG. 1 is a
visible side.
[0239] As illustrated in FIG. 1, the retardation film 3 is
preferably used as a polarizing plate protective film on a side on
which the cellulose acylate film of the present invention is not
used, and a retardation film in which various additives are blended
with the cellulose acylate film or a desired phase difference is
expressed by stretching, or a retardation film including an optical
anisotropic layer formed of a liquid-crystal composition on the
surface of the support is exemplified as this retardation film.
Specifically, the retardation film is able to refer to a
retardation film disclosed in JP2008-262161 A, and the contents are
incorporated herein.
[0240] In addition, for example, a polarizer in which a polyvinyl
alcohol film is dipped in an iodine solution and is stretched is
able to be used as the polarizer. When the polarizer in which the
polyvinyl alcohol film is dipped in the iodine solution and is
stretched is used, the surface treated surface of the cellulose
acylate film of the present invention is able to be directly bonded
to at least one surface of the polarizer by using an adhesive
agent. An aqueous solution of polyvinyl alcohol or polyvinyl acetal
(for example, polyvinyl butyral), latex of a vinyl-based polymer
(for example, polybutyl acrylate), and a curable adhesive agent
composition containing an epoxy compound which is cured by
irradiation of an active energy ray or heat are able to be used as
the adhesive agent described above. It is particularly preferable
that the adhesive agent is an aqueous solution of completely
saponified polyvinyl alcohol.
[0241] It is preferable that the polarizing plate protective film
of present invention is bonded to the polarizer such that a
transmission axis of the polarizer and a slow axis of the
polarizing plate protective film described above are orthogonal to
each other, parallel to each other, or at an angle of 45.degree..
The slow axis is able to be measured by various known methods, and
for example, is able to be measured by using a birefringence meter
(KOBRA DH, manufactured by Oji Scientific Instruments). Here, in
the present invention, the descriptions about an angle include a
range of error which is allowable in the art to which the present
invention belongs. For example, the expressions "orthogonal" and
"parallel" indicates that the angle is in a range of less than
.+-.100 from an exact angle relevant to parallel and orthogonal,
and an error from the exact angle is preferably less than or equal
to 5.degree., and is more preferably less than or equal to
3.degree..
[0242] Setting the transmission axis of the polarizer layer and the
slow axis of the polarizing plate protective film to be parallel to
each other indicates that the direction of the main refractive
index nx of the polarizing plate protective film and the direction
of the transmission axis of the polarizing plate intersect with
each other at an angle of .+-.10.degree.. The angle is preferably
within 5.degree., is more preferably within 3.degree., is even more
preferably within 1.degree., and is most preferably within
0.5.degree..
[0243] In addition, setting the transmission axis of the polarizer
and the slow axis of the polarizing plate protective film to be
orthogonal to each other indicates that the direction of the main
refractive index nx of the polarizing plate protective film and the
direction of the transmission axis of the polarizer intersect with
each other at an angle of 90.degree..+-.10.degree.. The angle is
preferably 90.degree..+-.5.degree., is more preferably
90.degree..+-.3.degree., is even more preferably
90.degree..+-.1.degree., and is most preferably
90.degree..+-.0.5.degree.. By setting the error to be within 10, a
decrease in performance of a polarization degree under
crossed-Nicols rarely occurs, and light leakage rarely occurs.
[0244] <Functionalization of Polarizing Plate>
[0245] It is preferable that the polarizing plate of the present
invention is used as a functionalized polarizing plate which is
combined with an antireflection film and a brightness enhancement
film for improving visibility of a display, or an optical film
including a functional layer such as a hard coat layer, a forward
scattering layer, and an anti-glare layer, within a range not
departing from the gist of the present invention. The details
thereof are able to refer to the description in paragraphs 0229 to
0242 and paragraphs 0249 to 0250 of JP2012-082235A and in
paragraphs 0086 to 0103 of JP2012-215812A, and the contents are
incorporated herein.
[0246] <Hard Coat Layer>
[0247] A hard coat layer which is preferably disposed on the
cellulose acylate film as necessary is a layer for applying
hardness or scratch resistance to the polarizing plate of the
present invention. For example, a coating composition is applied
onto the cellulose acylate film and is cured, and thus the hard
coat layer is able to be formed on the cellulose acylate film. A
filler or an additive is added to the hard coat layer, and thus
mechanical performance, electrical performance, optical
performance, physical performance, or chemical performance such as
water repellency and oil repellency is able to be applied to the
hard coat layer itself. The thickness of the hard coat layer is
preferably in a range of 0.1 .mu.m to 6 .mu.m, and is more
preferably in a range of 3 .mu.m to 6 .mu.m. By including a thin
hard coat layer in such a range, a polarizing plate including the
hard coat layer is obtained in which physical properties such as
suppression of brittleness or curling are enhanced, and a reduction
in weight and a reduction in manufacturing costs are realized.
[0248] It is preferable that the hard coat layer is formed by
curing a curable composition. It is preferable that the curable
composition is prepared as a liquid-like coating composition. An
example of such a coating composition contains a monomer or an
oligomer for a matrix forming binder, polymers, and an organic
solvent. This coating composition is cured after being coated, and
thus the hard coat layer is able to be formed. In the curing, a
cross-linking reaction or a polymerization reaction is able to be
used. The details thereof are able to refer to the description in
paragraphs 0088 to 0101 of JP2012-215812A, and the contents are
incorporated herein.
[0249] A curable composition which is particularly preferable for
forming the hard coat layer is a composition containing a
(meth)acrylate-based compound as used in examples described
below.
[0250] It is preferable that the curable composition is prepared as
a coating liquid. The coating liquid is able to be prepared by
dissolving and/or dispersing the component described above in an
organic solvent.
[0251] (Properties of Hard Coat Layer)
[0252] It is preferable that the hard coat layer formed on the
cellulose acylate film has high adhesiveness with respect to the
cellulose acylate film. In the hard coat layer formed of the
preferred curable composition described above on the cellulose
acylate film containing the compound described above, the curable
composition is able to exhibit high adhesiveness with respect to
the cellulose acylate film along with the compound described above.
The polarizing plate of the present invention includes such a
cellulose acylate film and a hard coat layer, and thus it is
possible to maintain adhesiveness between the cellulose acylate
film and the hard coat layer even when light irradiation or the
like is performed, and it is possible to exhibit excellent optical
durability.
[0253] It is preferable that the hard coat layer has excellent
scratch resistance. Specifically, when a pencil hardness test which
is an index of scratch resistance is performed, it is preferable
that hardness of greater than or equal to 3H is attained.
[0254] <Liquid-Crystal Display Device>
[0255] A liquid-crystal display device of the present invention
includes at least one polarizing plate of the present invention.
The details of the liquid-crystal display device are able to refer
to the description in paragraphs 0251 to 0260 of JP2012-082235A,
and the contents are incorporated herein.
EXAMPLES
[0256] Hereinafter, the present invention will be more specifically
described with reference to examples. Materials, used amounts,
ratios, treatment contents, treatment sequences, and the like of
the following examples are able to be suitably changed unless the
changes cause deviance from the gist of the present invention.
Accordingly, the range of the present invention is not limited to
the following specific examples.
[0257] Identification of all synthesized compounds was performed by
using one or more of .sup.1H-NMR (300 MHz), Matrix-Assisted Laser
Desorption/Ionization Time of Flight Mass Spectrometry
(MALDI-TOF-MS), and Liquid Chromatography/Mass Spectrometry
(LC/MS). In addition, a melting point was measured by using a trace
melting point measure device (MP-500D, manufactured by Yanaco New
Science Inc.).
[0258] The following compound numbers are the numbers of the
exemplary compounds described above.
Synthesis Example 1
Synthesis of Compound 1-9
[0259] 107 g (1.5 mol) of cyano ethanol, 200 mg of n-dibutyl tin
diacetate, and 750 mL of ethyl acetate were put into a three-neck
flask of 2 L which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and 100 ml. of
an ethyl acetate solution of 167 g (0.75 mol) of isophorone
diisocyanate was dripped into the three-neck flask for 30 minutes
under ice cooling. After that, a reaction was performed at
50.degree. C. for 4 hours. A reaction mixture was concentrated, and
was purified by silica gel column chromatography (a solvent of
ethyl acetate/n-hexane) to be a white solid, and thus 189 g of a
compound 1-9 was obtained (a yield of 70%).
[0260] MALDI-TOF-MS: M+Na; 387
Synthesis Example 2
Synthesis of Mixture of Compound 2-2-A and Compound 2-2-B
[0261] 44.4 g (0.20 mol) of isophorone diisocyanate and 150 mL of
THF were put into a three-neck flask which was attached with a
mechanical stirrer, a thermometer, a cooling pipe, and a dripping
funnel, and 50 mL of a THF solution of 24.6 g (0.25 mol) of imino
dipropionitrile was dripped into the flask at room temperature of
lower than or equal to 10.degree. C. After that, the mixture was
stirred at 60.degree. C. for 4 hours, and then 10 mg of n-dibutyl
tin diacetate and 27.6 g (0.20 mol) of phenoxy ethanol were dripped
into the mixture at room temperature, and a reaction was further
performed at 60.degree. C. for 4 hours. A solvent was concentrated
after the reaction ended, and the mixture was purified by silica
gel column chromatography (a solvent of ethyl
acetate/n-hexane/methanol), and thus 34 g of a mixture of a
compound 2-2-A and a compound 2-2-B was obtained as a glass-like
solid (a yield of 35%).
[0262] MALDI-TOF-MS M+Na: 507
Synthesis Example 3
[0263] A compound 1-16, a compound 1-14, a compound 1-3, and a
compound 1-6 were synthesized by the same method as that in
Synthesis Example 1 except that the cyano ethanol in the synthesis
of the compound 1-9 was changed to N-(2-hydroxy ethyl) succinimide,
N-(2-hydroxy ethyl) hexahydroxy phthalimide, imino dipropionitrile,
and imino diacetonitrile.
Synthesis Example 4
[0264] A compound 1-7 was synthesized by the same method as that in
Synthesis Example 1 except that the isophorone diisocyanate in the
synthesis of the compound 1-9 was changed to xylylene
diisocyanate.
Synthesis Example 5
[0265] A mixture of a compound 2-3-A and a compound 2-3-B, and a
compound 3-7 were synthesized by the same method as that in
Synthesis Example 2 except that the imino dipropionitrile in the
synthesis of the mixture of the compound 2-2-A and the compound
2-2-B is changed to imino diacetonitrile and methyl glycine.
Synthesis Example 6
[0266] A compound 1-11, a mixture of a compound 2-5-A and a
compound 2-5-B, a mixture of a compound 2-6-A and a compound 2-6-B,
a compound 3-1, a compound 3-9, a compound 3-13, a compound 3-20, a
compound 3-21, and a compound 3-22 were synthesized by the same
method as that in any one of Synthesis Examples 1 to 5 except that
diisocyanate, alcohol, and amine which were raw materials were
suitably changed.
Synthesis Example 7
Synthesis of Compound 4-1-A
##STR00031##
[0268] (Et: Ethyl Group)
[0269] 79.5 g (1.06 mol) of 1-amino-2-propanol, 80.3 g (0.79 mol)
of triethyl amine, and 700 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, and a dripping funnel, and were cooled to 0.degree.
C., and a mixed solution of 50 g (0.53 mol) of methyl chloroformate
and 50 ml of ethyl acetate was dripped into the flask. The mixture
was stirred for 30 minutes, and then 400 ml of water and 75 ml of a
concentrated hydrochloric acid were added to the mixture, liquid
separation was performed, and then 200 ml of water was added to the
mixture, and the liquid separation was performed again. An organic
layer was subjected to a dehydration treatment with sodium sulfate,
filtration, and solvent concentration, and thus 52.9 g of a
compound 4-1-A was obtained (a yield of 75%).
Synthesis of Compound 4-1
[0270] 21.3 g (0.11 mol) of metaxylylene diisocyanate, 0.36 g of
dibutyl tin dilaurate, and 115 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 18.1 g (0.14 mol) of the compound 4-1-A was
dripped into the flask. The mixture was stirred at room temperature
for 3 hours, and then 2.9 g of methanol was added to the mixture,
and was stirred for 4 hours.
[0271] An educed white solid was filtered after the reaction ended,
and was purified by silica gel column chromatography (a solvent of
ethyl acetate/n-hexane/methanol), and thus 26.3 g of a compound 4-1
was obtained as the white solid (a yield of 66%).
[0272] .sup.1H-NMR (CDCl.sub.3) .delta.1.2 (d, J=7.5 Hz, 3H),
3.5-3.2 (br, 2H), 3.6 (s, 3H), 3.7 (s, 3H), 4.4 (m, 4H), 5.1-4.8
(br, 4H), 7.2 (m, 3H), 7.3 (m, 1H)
[0273] LC/MS(ESI(+)): 376.4[M+Na]
Synthesis of Compound 4-2
[0274] 30.1 g (0.23 mol) of the compound 4-1-A, 0.36 g of dibutyl
tin dilaurate, and 115 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 21.3 g (0.11 mol) of metaxylylene diisocyanate
was dripped into the flask. The mixture was stirred at room
temperature for 4 hours, and then 2.0 g of methanol was added to
the mixture, and was stirred for 1 hour.
[0275] An educed white solid was filtered after the reaction ended,
and was purified by silica gel column chromatography (a solvent of
ethyl acetate/n-hexane/methanol), and thus 46.5 g of a compound 4-2
was obtained as the white solid (a yield of 93%).
[0276] .sup.1H-NMR (CDCl.sub.3) .delta.1.2 (d, J=7.5 Hz, 6H),
3.5-3.2 (br, 4H), 3.6 (s, 6H), 4.3 (m, 4H), 5.1-4.9 (br, 4H), 7.2
(m, 3H), 7.3 (m, 1H)
[0277] LC/MS(ESI(+)): 355.3 [M+H]
Synthesis Example 8
Synthesis of Compound 4-3
[0278] A compound 4-3 was synthesized by the same method as that in
the synthesis of the compound 4-1 in Synthesis Example 7 except
that the 1-amino-2-propanol in the synthesis of the compound 4-1-A
was changed to 1-aminoethanol.
Synthesis of Compound 4-4
[0279] A compound 4-4 was synthesized by the same method as that in
the synthesis of the compound 4-2 in Synthesis Example 7 except
that the 1-amino-2-propanol in the synthesis of the compound 4-1-A
was changed to 1-aminoethanol.
Synthesis Example 9
Synthesis of Compound 4-5-A
##STR00032##
[0281] (Me: Methyl Group)
[0282] 51.0 g (0.50 mol) of propylene carbonate was put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, and a dripping funnel, and 61 ml (0.60 mol) of methyl
amine [40% of a methanol solution] was dripped into the flask while
being stirred at room temperature. The mixture was stirred at room
temperature for 3 hours, and then vacuum concentration for removing
excessive methyl amine was performed, and thus 65.9 g of a compound
4-5-A was obtained as a colorless liquid (a yield of 99%).
Synthesis of Compound 4-5
[0283] A compound 4-5 was synthesized by the same method as that in
Synthesis Example 7 except that the compound 4-1-A which was the
raw material in the synthesis of the compound 4-1 was changed to
the compound 4-5-A.
Synthesis of Compound 4-6
[0284] A compound 4-6 was synthesized by the same method as that in
Synthesis Example 7 except that the compound 4-1-A which was the
raw material in the synthesis of the compound 4-2 was changed to
the compound 4-5-A (a yield of 64%).
[0285] .sup.1H-NMR (DMSO-d6) .delta.1.2 (m, 6H), 2.6 (s, 6H), 4.0
(m, 4H), 4.1 (d, J=6.3 Hz, 4H), 4.8 (m, 2H), 7.0 (s, 1H), 7.1 (m,
4H), 7.2 (m, 1H), 7.8-7.7 (br, 2H)
[0286] LC/MS(ESI(+)): 477.4[M+Na]
Synthesis Example 10
Synthesis of Compound 4-7
[0287] A compound 4-7 was synthesized by the same method as that in
the synthesis of the compound 4-5 in Synthesis Example 9 except
that the methyl amine in the synthesis of the compound 4-5-A was
changed to ethyl amine.
Synthesis of Compound 4-8
[0288] A compound 4-8 was synthesized by the same method as that in
the synthesis of the compound 4-6 in Synthesis Example 9 except
that the methyl amine in the synthesis of the compound 4-5-A was
changed to ethyl amine.
Synthesis of Compound 4-9
[0289] A compound 4-9 was synthesized by the same method as that in
the synthesis of the compound 4-5 in Synthesis Example 9 except
that the methyl amine in the synthesis of the compound 4-5-A was
changed to isopropyl amine.
Compound 4-10
[0290] A compound 4-10 was synthesized by the same method as that
in the synthesis of the compound 4-6 in Synthesis Example 9 except
that the methyl amine in the synthesis of the compound 4-5-A was
changed to isopropyl amine.
Synthesis of Compound 4-12-B
##STR00033##
[0292] 50.0 g (0.32 mol) of cis-1,2-cyclohexane dicarboxylic
anhydride and 330 mL of toluene were put into a three-neck flask
which was attached with a mechanical stirrer, a thermometer, and a
dripping funnel, and 19.8 g (0.32 mol) of 2-aminoethanol was
dripped into the flask. The mixture was stirred at 130.degree. C.
for 3 hours, and then was cooled to room temperature. 200 mL of
ethyl acetate and 200 mL of a hydrochloric acid of 1 N
concentration were added to the mixture, liquid separation was
performed, and then 1 L of water and 0.5 L of a saturated saline
solution were further added to the mixture, and the liquid
separation was performed again. An organic layer was subjected to a
dehydration treatment with sodium sulfate, filtration, and solvent
concentration, and thus 62.9 g of a compound 4-12-B was obtained (a
yield of 98%).
Synthesis Example 11
Synthesis of Compound 4-11
[0293] 21.3 g (0.11 mol) of metaxylylene diisocyanate, 0.36 g of
dibutyl tin dilaurate, and 115 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 18.6 g (0.14 mol) of the compound 4-5-A was
dripped into the flask. The mixture was stirred at room temperature
for 3 hours, and 7.8 g (0.11 mol) of cyano ethanol was added to the
mixture, and was stirred for 4 hours.
[0294] An educed white solid was filtered after the reaction ended,
and was purified by silica gel column chromatography (a solvent of
ethyl acetate/n-hexane/methanol), and thus 29.3 g of a compound
4-11 was obtained as the white solid (a yield of 68%).
[0295] .sup.1H-NMR (DMSO-d6) 61.2 (m, 3H), 2.6 (s, 3H), 2.8 (m,
2H), 4.2-4.0 (m, 8H), 4.8 (m, 1H), 7.1-7.0 (m, 4H), 7.3-7.2 (m,
2H), 7.8-7.7 (br, 1H)
Synthesis of Compound 4-12
[0296] A compound 4-12 was synthesized by the same method as that
in the synthesis of the compound 4-11 except that the cyano ethanol
in the synthesis of the compound 4-11 was changed to the compound
4-12-B.
Synthesis Example 12
Synthesis of Compound 5-1
[0297] 49.8 g (0.22 mol) of isophorone diisocyanate, 0.71 g of
dibutyl tin dilaurate, and 225 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 35.8 g (0.27 mol) of the compound 4-1-A was
dripped into the flask. The mixture was stirred at 45.degree. C.
for 3 hours, and then 5.7 g of methanol was added to the mixture,
and was stirred for 4 hours. A reaction mixture was concentrated
after the reaction ended, and was purified by silica gel column
chromatography (a solvent of ethyl acetate/n-hexane/methanol), and
thus 26.9 g of a compound 5-1 was obtained as a glass-like solid (a
yield of 31%).
[0298] .sup.1H-NMR (DMSO-d6) .delta.1.1-0.8 (br, 16H), 1.5-1.3 (br,
2H), 2.7 (m, 2H), 3.1 (m, 2H), 3.5 (br, 7H), 4.6 (Hex, J=6.3 Hz,
1H), 7.2-6.7 (br, 3H)
[0299] LC/MS(ESI(+)): 410.4[M+Na]
Synthesis of Compound 5-2
[0300] 58.2 g (0.44 mol) of the compound 4-1-A, 0.36 g of dibutyl
tin dilaurate, and 115 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 49.8 g (0.22 mol) of isophorone diisocyanate
was dripped into the flask. The mixture was stirred at 60.degree.
C. for 6 hours, and then 2.0 g of methanol was added to the
mixture, and was stirred for 1 hour.
[0301] A reaction mixture was concentrated after the reaction
ended, and was purified by silica gel column chromatography (a
solvent of ethyl acetate/n-hexane/methanol), and thus 97.5 g of a
compound 5-2 was obtained as a glass-like solid (a yield of
89%).
[0302] .sup.1H-NMR (DMSO-d6) .delta.1.1-0.8 (br, 19H), 1.5-1.3 (br,
2H), 2.7 (m, 2H), 3.1 (m, 4H), 3.5 (br, 7H), 4.6 (Hex, J=6.3 Hz,
2H), 7.2-6.7 (br, 4H)
[0303] LC/MS(ESI(+)): 489.4[M+H]
Synthesis Example 13
[0304] A compound 5-3 and a compound 5-4 were synthesized by the
same method as that in Synthesis Example 12 except that the
1-amino-2-propanol in the synthesis of the compound 5-1 and the
compound 5-2 was changed to 1-aminoethanol.
Synthesis Example 14
Synthesis of Compound 5-5
[0305] A compound 5-5 was synthesized by the same method as that in
Synthesis Example 12 except that the compound 4-1-A in the
synthesis of the compound 5-1 was changed to the compound
4-5-A.
Synthesis of Compound 5-6
[0306] A compound 5-6 was synthesized by the same method as that in
Synthesis Example 12 except that the compound 4-1-A in the
synthesis of the compound 5-2 was changed to the compound
4-5-A.
[0307] .sup.1H-NMR (DMSO-d6) .delta.1.2-0.8 (br, 19H), 1.5-1.4 (br,
2H), 2.5 (m, 6H), 2.8-2.6 (br, 2H), 3.7-3.5 (br, 1H), 4.0-3.9 (br,
4H), 4.9-4.7 (br, 2H), 7.3-6.8 (br, 4H)
[0308] LC/MS(ESI(+)): 511.4[M+Na]
Synthesis Example 15
[0309] A compound 5-7, a compound 5-8, a compound 5-9, and a
compound 5-10 were synthesized by the same method as that in
Synthesis Example 14 except that the methyl amine in the synthesis
of the compound 4-5-A was changed to ethyl amine and isopropyl
amine.
Synthesis Example 16
Synthesis of Compound 5-11
[0310] 24.5 g (0.11 mol) of isophorone diisocyanate, 0.36 g of
dibutyl tin dilaurate, and 115 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and 18.6 g (0.14 mol) of the compound 4-5-A was
dripped into the flask. The mixture was stirred at room temperature
for 3 hours, and then 7.8 g (0.11 mol) of cyano ethanol was added,
and was stirred for 4 hours.
[0311] The mixture was purified by silica gel column chromatography
(a solvent of ethyl acetate/n-hexane/methanol) after the reaction
ended, and thus 30.5 g of a compound 5-11 was obtained (a yield of
65%).
[0312] .sup.1H-NMR (DMSO-d6) .delta.1.2-0.8 (br, 161H), 1.5-1.4
(br, 2H), 2.5 (m, 3H), 2.8-2.6 (m, 4H), 3.7-3.6 (br, H), 4.1-3.9
(m, 4H), 4.9-4.7 (br, 1H), 7.3-6.8 (br, 3H)
Synthesis of Compound 5-12
[0313] A compound 5-12 was synthesized by the same method as that
in the synthesis of the compound 5-11 except that the cyano ethanol
in the synthesis of the compound 5-11 was changed to the compound
4-12-B.
Synthesis Example 17
Synthesis of Compound 6-1
[0314] 88.9 g (0.40 mol) of isophorone diisocyanate, 1.3 g of
dibutyl tin dilaurate, and 500 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and a mixed solution of 15.4 g (0.48 mol) of
methanol and 30 mL of ethyl acetate was dripped into the flask. The
mixture was stirred at 0.degree. C. for 1.5 hours, and then was
heated to 60.degree. C., a mixed solution of 6.1 g (0.08 mol) of
1,2-propane diol and 30 mL of ethyl acetate was added to the
mixture, and was stirred for 4 hours. The mixture was purified by
silica gel column chromatography (a solvent of ethyl
acetate/n-hexane) after the reaction ended, and thus 12.5 g of a
compound 6-1 was obtained as a glass-like solid (a yield of
10%).
[0315] .sup.1H-NMR (DMSO-d6) .delta.1.2-0.8 (br, 33H), 1.7-1.3 (br,
5H), 2.7 (m, 3H), 3.7-3.4 (br, 8H), 4.0 (m, 1H), 4.8 (s, 1H),
7.2-6.8 (br, 4H)
Synthesis Example 18
[0316] A compound 6-2 was synthesized by the same method as that in
Synthesis Example 17 except that the isophorone diisocyanate in the
synthesis of the compound 6-1 was changed to metaxylylene
diisocyanate (a yield of 14%).
[0317] .sup.1H-NMR (DMSO-d6) .delta.1.2-1.0 (br, 3H), 3.5 (s, 6H),
4.2-4.0 (br, 10H), 4.9 (m, 1H), 7.3-7.1 (br, 8H), 7.8-7.6 (m,
4H)
Synthesis Example 19
[0318] A compound 6-3 was synthesized by the same method as that in
Synthesis Example 17 except that the isophorone diisocyanate and
the methanol in the synthesis of the compound 6-1 were changed to
metaxylylene diisocyanate and 2-cyano ethanol (a yield of 5%).
[0319] .sup.1H-NMR (DMSO-d6) .delta.1.3-1.0 (br, 3H), 2.8 (t, 4H),
4.3-4.0 (br, 19H), 4.9 (m, 1H), 7.3-7.1 (br, 8H), 8.0-7.6 (br,
4H)
Synthesis Example 20
Synthesis of Compound 6-4-A
[0320] 114.1 g (1.50 mol) of 1,2-propane diol, 0.9 mL (1.5 mmol) of
dibutyl tin dilaurate, and 500 ml of ethyl acetate were put into a
three-neck flask which was attached with a mechanical stirrer, a
thermometer, a cooling pipe, and a dripping funnel, and were cooled
to 0.degree. C., and a mixed solution of 56.5 g (0.30 mol) of
metaxylylene diisocyanate and 100 mL of ethyl acetate was dripped
into the flask. The mixture was stirred at 0.degree. C. for 1.5
hours, and was placed in a room temperature environment (25.degree.
C.), and thus the temperature of the mixture returned to room
temperature.
[0321] A reaction liquid was washed with 200 mL of water, and then
was washed with 200 mL of water and 100 mL of a saturated saline
solution two times. The reaction liquid was dried with magnesium
sulfate, and was concentrated, and thus 83.5 g of a compound 6-4-A
was obtained as a colorless liquid (a yield of 82%).
Synthesis of Compound 6-4
[0322] 56.5 g (0.30 mol) of metaxylylene diisocyanate, 0.9 mL (1.5
mmol) of dibutyl tin dilaurate, and 300 ml of ethyl acetate were
put into a three-neck flask which was attached with a mechanical
stirrer, a thermometer, a cooling pipe, and a dripping funnel, and
were cooled to 0.degree. C., and a mixed solution of 11.5 g (0.36
mol) of methanol and 30 mL of ethyl acetate was dripped into the
flask. The mixture was stirred at 0.degree. C. for 1.5 hours, and
then was heated to 60.degree. C., a mixed solution of 33.6 g (0.06
mol) of the compound 6-4-A and 130 mL of ethyl acetate was added to
the mixture in two times, and was stirred for 4 hours. The mixture
was purified by silica gel column chromatography (a solvent of
ethyl acetate/n-hexane) after the reaction ended, and thus 12.1 g
of a compound 6-4 was obtained as a white solid (a yield of
5%).
[0323] .sup.1H-NMR (DMSO-d6) 81.3-1.0 (br, 6H), 3.6 (s, 6H),
4.3-4.0 (br, 17H), 4.9 (m, 2H), 7.3-7.1 (br, 12H), 8.0-7.6 (br,
6H)
Synthesis Example 21
Synthesis of Compound 6-5
[0324] 66.7 g (0.30 mol) of isophorone diisocyanate, 0.84 g of
Neostann U-600 (manufactured by NITTO KASEI CO., LTD.), and 170 ml
of ethyl acetate were put into a three-neck flask which was
attached with a mechanical stirrer, a thermometer, a cooling pipe,
and a dripping funnel, and were cooled to 0.degree. C., and a mixed
solution of 11.4 g (0.15 mol) of 1,2-propane diol and 30 mL of
ethyl acetate was dripped into the flask. The mixture was heated to
60.degree. C. after the dripping, and was stirred for 6 hours. The
mixture was cooled to 0.degree. C., and 14.4 g (0.45 mol) of
methanol was dripped into the mixture. The mixture was heated to
40.degree. C. after the dripping, and was stirred for 3 hours. A
reaction liquid was transported into 1.5 L of hexane, a
precipitated solid was filtered, was washed with 1 L of hexane, and
was dried, and thus 73.2 g of a compound 6-5 was obtained (a yield
of 94%).
[0325] Weight Average Molecular Weight (Mw: 1407)
Synthesis Example 22
Synthesis of Compound 6-6
[0326] 22.8 g (0.30 mol) of 1,2-propane diol, 1.1 g of Neostann
U-600 (manufactured by NITTO KASEI CO., LTD.), and 200 ml of ethyl
acetate were put into a three-neck flask which was attached with a
mechanical stirrer, a thermometer, a cooling pipe, and a dripping
funnel, and were cooled to 0.degree. C., and a mixed solution of
44.4 g (0.20 mol) of isophorone diisocyanate and 10 mL of ethyl
acetate was dripped into the flask. The mixture was heated to
60.degree. C. after the dripping, and was stirred for 6 hours. A
reaction liquid was transported into 1.5 L of hexane, and a
precipitated solid was filtered, was washed with 1 L of hexane, and
was dried, and thus 59.4 g of a compound 6-6 was obtained (a yield
of 90%).
[0327] Weight Average Molecular Weight (Mw: 1271)
Example 1
Film Formation of Cellulose Acylate Film
Preparation of Cellulose Acylate Solution
[0328] The following compositions were put into a mixing tank, each
component was dissolved by being stirred, and thus a cellulose
acylate solution was prepared.
TABLE-US-00002 Composition of Cellulose Acylate Solution Cellulose
Acylate Having Degree of Acetyl 100.0 parts by mass Substitution of
2.87 and Degree of Polymerization of 370 Compound Shown in Table 2
Described below 10.0 parts by mass Methylene Chloride (First
Solvent) 353.9 parts by mass Methanol (Second Solvent) 89.6 parts
by mass n-Butanol (Third Solvent) 4.5 parts by mass
[0329] The cellulose acylate solution prepared as described above
was casted by using a drum casting device. Peeling off was
performed in a state where the amount of residual solvent in a dope
was approximately 70 mass %, and drying was performed in a state
where the amount of residual solvent was 3 mass % to 5 mass %.
After that, the casted solution was transported between rolls of a
heat treatment device, and was further dried, and thus a cellulose
acylate film of Example 1 was obtained.
[0330] <Measurement of Surface Hardness of Cellulose Acylate
Film>
[0331] A sample surface fixed to a glass substrate was measured in
conditions of a loading time of 10 see, a creeping time of 5 sec,
an offloading time of 10 sec, and a maximum load of 50 mN by a
Knoop indenter in which the direction of a short axis of an
indenter was arranged to be parallel to the transport direction (a
longitudinal direction; a test direction in a pencil hardness test)
at the time of forming the cellulose acylate film using a "Fischer
Scope H100Vp type hardness meter" manufactured by Fischer
Instruments K. K. The hardness was calculated from a relationship
between the contact area of the indenter and the sample and the
maximum load which were obtained from an indentation depth, and the
average value of five points was set to surface hardness.
[0332] In addition, the sample surface fixed to the glass substrate
was measured in conditions of a loading time of 10 sec, a creeping
time of 5 sec, an offloading time of 10 sec, and an indentation
load of 50 mN by using a "Fischer Scope H100Vp type hardness meter"
manufactured by Fischer Instruments K. K. on the basis of a method
of JIS Z 2251, and the hardness was calculated from the
relationship between the contact area of the indenter and the
sample and the maximum load which were obtained from the
indentation depth. Furthermore, JIS Z 2251 was Japanese Industrial
Standards prepared on the basis of ISO4545.
[0333] Further, in the same indentation position, the Knoop
indenter was rotated by each 10.degree., Knoop hardness was
measured at 18 directions in total, and thus the minimum value was
obtained, and the minimum value was coincident with the surface
hardness which was measured by arranging the direction of the short
axis of the Knoop indenter described above to be parallel to the
transport direction (the longitudinal direction; the test direction
in the pencil hardness test) at the time of forming the cellulose
acylate film.
[0334] The unit was denoted by N/mm.sup.2, and the results of
evaluation performed according to the following criteria were shown
in Table.
[0335] A++: The Knoop hardness of greater than or equal to 230
N/mm.sup.2
[0336] A+: The Knoop hardness of greater than or equal to 220
N/mm.sup.2 and less than 230 N/mm.sup.2
[0337] A: The Knoop hardness of greater than or equal to 210
N/mm.sup.2 and less than 220 N/mm.sup.2
[0338] B: The Knoop hardness of greater than or equal to 200
N/mm.sup.2 and less than 210 N/mm.sup.2
[0339] C: The knoop hardness of greater than or equal to 190
N/mm.sup.2 and less than 200 N/mm.sup.2
[0340] D: The Knoop hardness of less than 190 N/mm.sup.2
[0341] <Evaluation Method of Photo-Coloration
Suppression>
[0342] Light irradiation was performed with respect to each of the
cellulose acylate films obtained as described above for 96 hours by
using a super xenon weather meter (SX75, manufactured by Suga test
Instruments Co., Ltd.), and the presence or absence of
photo-coloration was evaluated according to a change in a hue b*
before and after the irradiation. The evaluation was performed
according to the following criteria, and the results were shown in
Table.
[0343] The film hue b* was measured by using a spectrophotometer
UV3150 manufactured by Shimadzu Corporation. When the value of the
hue b* was increased on a minus side, a blue color of transmitted
light was increased, and when the value of the hue b* was increased
on a plus side, a yellow color of the transmitted light was
increased.
[0344] A: A change width of b* before and after the irradiation of
less than or equal to 0.1
[0345] B: The change width of b* before and after the irradiation
of greater than 0.1 and less than or equal to 0.25
[0346] C: The change width of b* before and after the irradiation
of greater than 0.25 and less than or equal to 0.40
[0347] D: The change width of b* before and after the irradiation
of greater than 0.40
[0348] <Evaluation Method of Volatility>
[0349] A compound shown in Table 2 was heated from room temperature
to 140.degree. C. by using a TG/DTA measurement device (TG/DTA7200
manufactured by Hitachi High-Tech Science Corporation), a change in
the mass of the compound at the time of being held at 140.degree.
C. for 1 hour was measured, and the volatility was determined in
the following conditions.
[0350] In Table, when the change amount obtained by the measurement
was less than or equal to 0.1%, the evaluation was denoted as
"Absent", and when the change amount obtained by the measurement
was greater than or equal to 0.1%, the evaluation was denoted as
"Present".
TABLE-US-00003 TABLE 2 Structure of Additive Number of Connecting
Type and Amount of Groups Additive Selected from Added Film
Performance Group Film Compound Amount Knoop Photo- Molecular
Described Equivalent No. Number (wt %*) Hardness coloration
Volatility Weight above Weight U Note 101 1-7 10 211 A A Absent 330
2 165 Example 102 1-9 10 232 A++ A Absent 364 2 182 Example 103
1-11 10 224 A+ A Absent 509 2 255 Example 104 1-14 10 220 A+ A
Absent 617 2 309 Example 105 1-16 10 229 A+ A Absent 509 2 255
Example 106 2-2-A 10 230 A ++ A Absent 484 2 242 Example 2-2-B 107
2-3-A 10 224 A+ A Absent 456 2 228 Example 2-3-B 108 2-5-A 10 220
A+ A Absent 388 2 194 Example 2-5-B 109 2-6-A 10 229 A+ A Absent
432 2 216 Example 2-6-B 110 3-1 10 212 A A Absent 375 2 188 Example
111 3-7 10 215 A A Absent 450 2 225 Example 112 Comparative 10 204
B D Absent 484 2 242 Comparative Compound A Example 113 Comparative
10 201 B C Present 221 1 221 Comparative Compound B Example 114
Comparative 10 * 340 2 170 Comparative Compound C Example 115
Absent 0 180 D A -- -- -- -- Comparative Example 116 4-6 10 215 A A
Absent 426 4 107 Example 117 4-10 10 211 A A Absent 483 4 121
Example 118 5-1 10 220 A+ A Absent 387 3 129 Example 119 5-2 10 224
A+ A Absent 489 4 122 Example 120 5-4 10 221 A+ A Absent 373 4 93
Example 121 5-6 10 229 A+ A Absent 489 4 122 Example 122 6-1 10 219
A A Absent 585 4 146 Example 123 6-2 10 227 A+ A Absent 516 4 129
Example 124 6-3 10 229 A+ A Absent 595 4 149 Example 125 6-5 10 212
A A Absent 1407 9.5 148 Example * A cellulose acetate solution
prepared. by adding a comparative compound C was not completely
dissolved, and thus a film was not able to be prepared. * wt % is
mass % of an additive with respect to 100 mass % of cellulose
aeylate. In a film in which two types of additives were used, the
mixture obtained in the synthesis example was used.
##STR00034##
[0351] A comparative compound A is a compound A-23 disclosed in
JP2005-272566A, a comparative compound B is a compound A-32
disclosed in JP2005-272566A, and a comparative compound C is a
compound (53) described in compounds disclosed in
JP2002-322294A.
[0352] The Knoop hardness is an index indicating the surface
hardness of the film. All of the compounds used in the examples are
able to form a film exhibiting higher surface hardness than the
comparative compounds A and B. It is considered that the compound
used in the example includes the connecting group selected from the
group described above along with the polar group, and thus
suppresses the movement of a molecular chain of the cellulose
acylate, and contributes to improvement in the surface hardness.
More specifically, it is assumed that a proton position in the
connecting group selected from the group described above
effectively acts on an ester bond or a hydroxyl group of the
cellulose acylate and forms a hydrogen bond, and thus contributes
to suppression of the movement of the molecular chain of the
cellulose acylate. In contrast, it is assumed that the reason that
the comparative compounds A and B have a less surface hardness
improvement effect of the cellulose acylate film than the compound
used in the example is because the compounds of a comparative
example do not have a polar group (the residue of the compound
having C log P of less than or equal to 0.85).
[0353] In addition, as shown in Table 2, in all of the films of the
examples, the photo-coloration was sufficiently suppressed. It is
considered that a substituent group adjacent to an oxygen atom or a
nitrogen atom of the connecting group selected from the group
described above considerably contributes to suppression of the
photo-coloration. The present inventors have considered that the
reason that the photo-coloration is suppressed in the film of the
example is because an aromatic ring is not directly bonded to the
oxygen atom or the nitrogen atom of the connecting group selected
from the group described above.
[0354] In contrast, in the film of a comparative example containing
the comparative compound A, it is considered that the reason that
the evaluation result relevant to the suppression of the
photo-coloration is D is because the oxygen atom and the nitrogen
atom of the connecting group selected from the group described
above are directly bonded to a benzene ring.
[0355] Further, from the results shown in Table 2, it is possible
to confirm that the compound added to the film of the example has
small volatility, and thus is able to manufacture a cellulose
acylate film having excellent transparency. In contrast, the
comparative compound B had inferior volatility. The present
inventors have assumed that a difference in the volatility between
the compound added to the film of the example and the comparative
compound B mainly depends on a difference in the molecular
weights.
[0356] In contrast, the comparative compound C had inferior
compatibility with respect to the cellulose acylate, and thus was
able to prepare a film. It is considered that this is mainly
because the comparative compound C does not have a polar group. In
addition, a compound having two or more bivalent connecting groups
denoted by --NH--(C.dbd.O)--NH-- in the molecules, such as the
comparative compound C tends to have inferior compatibility with
respect to the cellulose acylate, and thus it is preferable that in
the present invention, the compound added to the cellulose acylate
film does not have a bivalent connecting group denoted by
--NH--(C.dbd.O)--NH-- in one molecule or has only one bivalent
connecting group denoted by --NH--(C.dbd.O)--NH-- in one
molecule.
[0357] From the results, it is possible to confirm that the film of
the example is a cellulose acylate film having high surface
hardness and reduced photo-coloration, and the compound added to
the film of the example has reduced volatilization.
Example 1-2
[0358] A cellulose acylate film was prepared by the same method as
that in Example 1 except that the type and the added amount of each
of the additives were changed as shown in Table described
below.
[0359] Each of the properties was evaluated by the same method as
that in Example 1.
TABLE-US-00004 TABLE 3 Added Film Performance Film Compound Amount
Knoop Photo- No. Number (wt %*) Hardness coloration Volatility Note
201 1-9 5 210 A A Absent Example 202 1-9 20 246 A++ A Absent
Example 203 2-6-A 5 210 A A Absent Example 2-6-B 204 2-6-A 7.5 224
A+ A Absent Example 2-6-B *wt % is mass % of an additive with
respect to 100 mass % of cellulose acylate. In a film in which two
types of additives were used, the mixture obtained in the synthesis
example was used.
[0360] As it is obvious from Table 3, the compound described above
is able to improve the surface hardness of the film by increasing
the added amount. In addition, even when the additive is added in a
small amount (a film 201 and a film 203), the surface hardness is
considerably improved compared to the comparative compound or a
film to which the additive is not added, and the range of the
amount of additive able to be added is broad.
Example 2
[0361] A cellulose acylate film was prepared by the same method as
that in Example 1 except that the degree of substitution of the
cellulose acylate and the type of each of the additives were
changed as shown in Table described below.
[0362] Each of the properties was evaluated by the same method as
that in Example 1.
[0363] The value of the Knoop hardness of each of the films was
evaluated in the following criteria, compared to the value of the
Knoop hardness of the film which was prepared without being added
with the additive.
[0364] A: Greater than or equal to 1.15 times the value of the
Knoop hardness at the time of not adding the additive
[0365] B: Greater than or equal to 1.05 times and less than 1.15
times the value of the Knoop hardness at the time of not adding the
additive
[0366] C: Greater than or equal to 1.00 times and less than 1.05
times the value of the Knoop hardness at the time of not adding the
additive
[0367] D: Less than 1.00 times the value of the Knoop hardness at
the time of not adding the additive
TABLE-US-00005 TABLE 4 Cellulose Acylate Additive Film Film
Performance Film Degree of Acetyl Compound Added Amount Thickness
Knoop Photo- No. Substitution Number (wt %*) (.mu.m) Hardness
coloration Volatility Note 301 2.42 1-9 10 52 A A Absent Example
302 2.42 1-14 10 60 B A Absent Example 303 2.77 2-3-A 10 63 A A
Absent Example 2-3-B 304 2.93 1-9 10 55 A B Absent Example 305 2.93
1-14 10 57 B A Absent Example 306 2.93 2-3-A 10 56 A A Absent
Example 2-3-B 307 2.87 3-9 10 62 A A Absent Example 308 2.87 3-13
10 61 A A Absent Example 309 2.87 3-20 10 59 A A Absent Example 310
2.87 3-21 10 63 A A Absent Example 311 2.87 3-22 10 62 A A Absent
Example *wt % is mass % of an additive with respect to 100 mass %
of cellulose acylate. In a film in which two types of additives
were used, the mixture obtained in the synthesis example was
used.
[0368] As shown in Table 4, in the compound described above, it was
found that preferred surface hardness was able to be expressed
without depending on the degree of substitution of the cellulose
acylate.
Example 3
[0369] A cellulose acylate film was prepared by the same method as
that in Example 1 except that the type of cellulose acylate, the
type of each of the additives, and the film thickness of the
cellulose acylate film were changed as shown in Table described
below.
[0370] Each of the properties was evaluated by the same method as
that in Example 1. Here, when the surface hardness was evaluated,
as described below, surface hardness of a film having a film
thickness of less than or equal to 40 m was measured by changing a
indentation load to 20 mN.
[0371] <Evaluation of Surface Hardness of Cellulose Acylate
Film>
[0372] The surface hardness of the cellulose acylate film obtained
as described above was measured by the same method as that in
Example 1 except that an indentation load was changed as described
above. The unit was denoted by N/mm.sup.2.
[0373] The value of the Knoop hardness of each of the films was
evaluated in the following criteria, compared to the value of the
Knoop hardness of the film which was prepared without being added
with the additive.
[0374] A: Greater than or equal to 1.15 times the value of the
Knoop hardness at the time of not adding the additive
[0375] B: Greater than or equal to 1.05 times and less than 1.15
times the value of the Knoop hardness at the time of not adding the
additive
[0376] C: Greater than or equal to 1.00 times and less than 1.05
times the value of the Knoop hardness at the time of not adding the
additive
[0377] D: Less than 1.00 times the value of the Knoop hardness at
the time of not adding the additive
TABLE-US-00006 TABLE 5 Cellulose Acylate Additive Film Film
Performance Film Degree of Acetyl Compound Added Amount Thickness
Knoop Photo- No. Substitution Number (wt %*) (.mu.m) Hardness
coloration Volatility Note 401 2.86 1-9 12 28 A A Absent Example
402 2.86 1-14 12 29 A A Absent Example 403 2.86 2-3-A 12 24 A A
Absent Example 2-3-B 404 2.86 1-9 12 42 B A Absent Example *wt % is
mass % of an additive with respect to 100 mass % of cellulose
acylate. In a film in which two types of additives were used, the
mixture obtained in the synthesis example was used.
[0378] As shown in Table 5, in the compound described above, it was
found that preferred surface hardness was able to be expressed even
when the film was thinned.
Example 4
Preparation of Optical Film Attached with Hard Coat Layer
[0379] A hard coat layer solution having the following curable
composition was applied onto the surface of an optical film of a
single layer formed of the cellulose acylate which was prepared in
each of Example 1 and Example 2 described above, and was cured by
ultraviolet irradiation, and thus an optical film attached with a
hard coat layer was prepared on which a hard coat layer having a
thickness of 6 .mu.m was formed.
TABLE-US-00007 Curable Composition of Hard Coat Layer Solution
Monomer Pentaerythritol Triacrylate/Pentaerythritol 53.5 parts by
mass Tetraacrylate (Mixed Mass Ratio of 3/2) Photopolymerization
Initiator Irgacure (Japanese 1.5 parts by mass Registered
Trademark) TM907 (manufactured by BASF SE) Ethyl Acetate 45 parts
by mass
[0380] (Pencil Hardness Evaluation)
[0381] The humidity of each of the cellulose acylate films attached
with a hard coat layer was adjusted for 2 hours in conditions of a
temperature of 25.degree. C. and relative humidity of 60%, and the
pencil hardness was measured by using a pencil for a test defined
in JIS-S6006 according to a pencil hardness evaluation method
defined in JIS-K5400 such that the surface of the hard coat layer
was repeatedly scratched 5 times with a pencil with each hardness
by using a weight of 500 g, and the hardness was measured until the
number of defects became 1. Furthermore, it is disclosed that a
defect defined in JIS-K5400 is a breakage of a coated film and a
scratch of the coated film, but concavity of the coated film is not
a target, but in this evaluation, the concavity of the coated film
was also determined as a defect. It is practically preferable the
pencil hardness is greater than or equal to 3H, and high hardness
is obtained as the numerical value becomes greater, and thus
increasing the numerical value is preferable. As a result thereof,
it was found that all of films Nos. 102, 104, 106, 107, 201, and
202 of the examples had high evaluation of 3H, compared to a film
No. 115 having evaluation of 2H to which the additive was not
added.
Example 5
Preparation of Polarizing Plate
[0382] Saponification Treatment of Polarizing Plate Protective
Film
[0383] Each of the cellulose acylate films which were obtained in
Example 1 was dipped in 2.3 mol/L of an aqueous solution of sodium
hydroxide at 55.degree. C. for 3 minutes. The cellulose acylate
film was washed in a water washing bath at room temperature, and
was neutralized at 30.degree. C. by using 0.05 mol/L of a sulfuric
acid. The cellulose acylate film was washed again in the water
washing bath at room temperature, and was further dried with hot
air at 100.degree. C. Thus, a saponification treatment was
performed with respect to the surface of the cellulose acylate
film.
[0384] Preparation of Polarizing Plate
[0385] Iodine was adsorbed in a stretched polyvinyl alcohol film,
and was aligned, and thus a polarizer was prepared.
[0386] The cellulose acylate film which had been subjected to the
saponification treatment was bonded to one side of the polarizer by
using a polyvinyl alcohol-based adhesive agent. A commercially
available cellulose triacetate film (Fujitac (Japanese Registered
Trademark) TD80UF, manufactured by Fujifilm Corporation) was also
subjected to the same saponification treatment, and was bonded to
the surface of the polarizer on a side opposite to the surface side
onto which the cellulose acylate film prepared as described above
was bonded by using the polyvinyl alcohol-based adhesive agent.
[0387] At this time, a transmission axis of the polarizer and a
slow axis of the obtained cellulose acylate film were arranged to
be parallel to each other. In addition, the transmission axis of
the polarizer and a slow axis of the commercially available
cellulose triacetate film were arranged to be orthogonal to each
other.
[0388] Thus, Each Polarizing Plate was Prepared.
[0389] <Evaluation of Polarizing Plate Durability>
[0390] A polarizing plate durability test was performed in a state
where the polarizing plate was bonded to glass through a
pressure-sensitive adhesives as follows.
[0391] Two samples (approximately 5 cm.times.5 cm) were prepared in
which the polarizing plate was bonded onto glass such that the
cellulose acylate film of the example prepared in Example 1 was on
an air boundary side. Orthogonal transmittance measurement of a
single plate was performed by setting a side of the cellulose
acylate film of the example obtained in Example 1 in this sample to
be directed towards a light source. The orthogonal transmittance of
the plate was measured in a range of 380 nm to 780 nm by using an
automatic polarizing film measurement device VAP-7070 manufactured
by Jasco Corporation, and a measured value at 410 nm was adopted.
Each of the two samples was measured, and the average value thereof
was set to orthogonal transmittance of the polarizing plate. After
that, each of the polarizing plates was aged and held for 120 hours
under an environment of a temperature of 80.degree. C. and relative
humidity of 90% RH, and the orthogonal transmittance was measured
by using the same method. A change in the orthogonal transmittance
before and after aging was obtained, and the change was evaluated
as the polarizing plate durability. Furthermore, relative humidity
under an environment where the humidity was not adjusted was in a
range of 0% RH to 20% RH.
[0392] It was found that in the film No. 102 and the film No. 104
of the example of Example 1, the change in the orthogonal
transmittance before and after aging decreased, and the added
compound improved the polarizing plate durability, compared to the
film No. 115 in which the additive was not included.
Example 6
Preparation of Liquid-Crystal Display Device
[0393] A polarizing plate on a visible side of a commercially
available liquid-crystal television (Bravia (Japanese Registered
Trademark) J5000, manufactured by SONY Corporation) was peeled off,
and each of the polarizing plates prepared in the examples was
bonded to the liquid-crystal television on an observer side through
a pressure-sensitive adhesives such that each of the polarizing
plate protective films of the examples was on a side opposite to
the liquid-crystal cell side, and thus a liquid-crystal display
device was obtained.
EXPLANATION OF REFERENCES
[0394] 1: cellulose acylate film [0395] 2: polarizer [0396] 3:
retardation film [0397] 4: liquid-crystal cell [0398] 10: upper
side polarizing plate
* * * * *